Patent Application
20080299312
The present invention relates to a raw material solution for MOCVD method, which is a single solution of metal materials when forming a composite oxide film containing Hf-Si such as a HfSiO film or a HfSiON film using a Metal Organic Chemical Vapor Deposition method (hereinafter, referred to as MOCVD method), and to a method for manufacturing composite oxide film containing Hf-Si using the raw material solution.
Silicon dioxide film is used as a high-k dielectric gate insulator, and thinning the silicon dioxide film is recently in progress to obtain a high density of LSI. However, since a tunnel current flows and an effect of insulation is decreased in a thin film having a thickness less than or equal to 100 nm, further thinning of the silicon oxide film is limited.
Therefore, a gate insulating film is considered in place of the silicon oxide film, and hafnium and silicon contained oxide films, specifically a composite oxide film containing Hf-Si such as a Hf-Si—O film or a Hf-Si—O—N film came to attention as a candidate. Examples of a method for producing a composite oxide film containing Hf-Si include a sputtering method, an ion plating method, a thermal decomposition, MOD (Metal Organic Deposition) such as a sol-gel process, and the like, and the most appropriate film production process is the MOCVD method considering its excellent composition control and step coverage in comparison with the above-mentioned production methods, and integrity with a semiconductor manufacturing process.
As a material for forming a composite oxide film containing Hf-Si, there are metal chloride or metal alkoxide, a DPM complex, and the like. As an organic Si compound, there are tetrakis(ethoxy)silane (hereinafter, referred to as Si(C2H5O)4) and SiCl6. As an organic Hf compound, there are tetrakis(tertiary-butoxy)hafnium (hereinafter, referred to as Hf(t-C3H7O)4), tetrakis(dipivaloylmethanate)hafnium (hereinafter, referred to as Hf(DPM)4), and the like.
However, there is a problem in the MOCVD method using a metalorganic compound that selection and composition of appropriate metalorganic compound raw materials are important, and there may always not be appropriate metalorganic compound raw materials for desired metal materials.
In order to solve such above-mentioned problem, there has been provided a method (e.g., see Patent Document 1) for forming a Hf-containing thin film according to the MOCVD method including a transport of at least one or plurality of metalorganic materials of M[N(C2H5)2]4 (M is a metal (Si containing) element) into a film forming chamber, a deposition of a metal (alloy containing) film or a metal compound film by a CVD method, and a thermal treatment followed by the deposition at a temperature higher than a volume temperature. According to the above-mentioned film forming method, although a film-forming surface of a semiconductor device or an electronic equipment is uneven, metal and a compound thereof can be deposited with excellent controllability and uniformity to manufacture a semiconductor device and an electronic equipment having an excellent performance.
[Patent Document 1] Japanese Unexamined Patent Application, First Publication No. 2002-167672 (claim 1, paragraph [0005])
However, since the thermal treatment for improving a film quality is required after depositing a desired metal compound film according to the above-mentioned film forming method disclosed in the Patent Document 1, a process is complicated, and a substrate can be damaged as the thermal treatment is performed at a higher temperature than the temperature required for a film deposition.
The object of the invention is to provide a raw material solution having a high film forming rate for the MOCVD method, and a production method for forming the composite oxide film containing Hf-Si by using the raw material solution.
The other object of the invention is to provide a method for manufacturing the composite oxide film containing Hf-Si having a good adhesivity with a substrate, by using the raw material solution for MOCVD method.
The invention according to claim 1 is a raw material solution for MOCVD method including an organic Si compound represented by the following formula (1) and an organic Hf compound represented by the following formula (2), which are mixed in a predetermined ratio to dissolve the organic Hf compound in the organic Si compound.
(R1R2N)nSiH(4-n) (1)
(wherein, R1 and R2 are straight or branched alkyl groups having 1 to 4 carbon atoms provided that R1 and R2 are same with each other, R1 is an alkyl group having 1 or 2 carbon atoms and R2 is a straight or branched alkyl group having 2 to 4 carbon atoms provided that R1 and R2 are different from each other, and n is an integer of 1 to 4).
Hf(OR3)4 (2)
(wherein, R3 is a straight or branched alkyl group having 1 to 4 carbon atoms).
The invention according to claim 1 is a single solution of the metalorganic compound raw material for a film containing a plurality of metals such as the composite oxide film containing Hf-Si, and is obtained by mixing the organic Si compound represented by the above-mentioned formula (1) with the organic Hf compound represented by the above-mentioned formula (2) in a predetermined ratio and then dissolving the organic Hf compound in the organic Si compound. Since the single solution of the raw material solution for MOCVD method prepared in such manner is seemed to include an intermediate of Hf-Si mixed metal polynuclear molecule formed with the organic Hf compound and the organic Si compound, this intermediate nucleates the initial film-forming core on a surface of the substrate. Therefore, high film forming rate is obtained by using the raw material solution of the invention.
The invention according to claim 2 is the raw material solution for metal organic chemical vapor deposition method according to claim 1, in which a mixing ratio of the organic Si compound and the organic Hf compound is within a range of 0.001 to 0.5 wt % in a weight ratio (organic Hf compound/organic Si compound).
The invention according to claim 2 forms the composite oxide film containing Hf-Si of high quality by using the raw material solution mixed within the above-mentioned ratio.
The invention according to claim 3 is a method for manufacturing composite oxide film containing Hf-Si including preparing of the composite oxide film containing Hf-Si by using the raw material solution for metal organic chemical vapor deposition method according to claim 1 or 2.
The invention according to claim 3 can form a film at a higher film forming rate by using the above-mentioned single solution of raw material solution for MOCVD method, in comparison with a conventional case where two solutions of raw material solutions for MOCVD method are respectively supplied to prepare a film, and further obtains the composite oxide film containing Hf-Si having a high adhesivity with a substrate.
The invention according to claim 4 is the method for manufacturing composite oxide film containing Hf-Si which includes the steps of growing a Si film on a surface of a substrate by thermally decomposing an organic Si compound having a same or different composition from the organic Si compound used for the raw material solution for metal organic chemical vapor deposition method according to claim 1 or 2 together with a reducing gas; and forming a HfSiO film on a surface of the grown Si film by supplying the raw material solution for metal organic chemical vapor deposition method according to claim 1 or 2 together with an oxidizing agent and performing the thermal decomposition.
The invention according to claim 4 further improves adhesivity of HfSiO film with a substrate by preparing the HfSiO film on a surface of the Si film grown in advance on a surface of a substrate.
The invention according to claim 5 is the method for manufacturing composite oxide film containing Hf-Si which includes the steps of growing a Si film on a surface of a substrate by thermally decomposing an organic Si compound having a same or different composition from the organic Si compound used for the raw material solution for metal organic chemical vapor deposition method according to claim 1 or 2 together with a reducing gas; and forming a HfSiON film on a surface of the grown Si film by supplying the raw material solution for metal organic chemical vapor deposition method according to claim 1 or 2 together with an oxidizing agent and a nitrogen source and then performing the thermal decomposition.
The invention according to claim 5 further improves adhesivity of HfSiON film with a substrate by preparing the HfSiON film on a surface of the Si film grown in advance on a surface of the substrate.
The invention according to claim 6 is a raw material solution for metal organic chemical vapor deposition method, which is prepared by mixing an organic Si compound with an organic Hf compound such that the mixing ratio ranges from 0.001 to 0.5 wt % in a weight ratio (organic Hf compound/organic Si compound); dissolving the organic Hf compound in the organic Si compound; and heating the solution at a temperature of 20 to 100° C.
The invention according to claim 6 is a raw material solution which is a single solution of the metalorganic compound raw material for a film containing a plurality of metals such as the composite oxide film containing Hf-Si. This raw material solution is prepared as a single solution by mixing the organic Si compound with the organic Hf compound in a predetermined mixing ratio and then by dissolving the organic Hf compound in the organic Si compound, and the solution is obtained by heating in a predetermined temperature range to be prepared. Since the single solution of the raw material solution for MOCVD method prepared in such manner is thought to include an intermediate of Hf-Si mixed metal polynuclear molecule formed with the organic Hf compound and the organic Si compound, this intermediate nucleates the initial film-forming core on a surface of the substrate. Therefore, high film forming rate is obtained by using the raw material solution of the invention.
The invention according to claim 7 is the raw material solution for metal organic chemical vapor deposition method according to claim 6, in which the organic Si compound is represented by the following formula (1) or (3).
(R1R2N)nSiH(4-n) (1)
(wherein, R1 and R2 are straight or branched alkyl groups having 1 to 4 carbon atoms provided that R1 and R2 are same with each other, R1 is an alkyl group having 1 or 2 carbon atoms and R2 is a straight or branched alkyl group having 2 to 4 carbon atoms provided that R1 and R2 are different from each other, and n is an integer of 1 to 4).
(R3O)mSiH(4-m) (3)
(wherein, R3 is a straight or branched alkyl group having 1 to 4 carbon atoms, and m is an integer of 1 to 4).
In the invention according to claim 7, the organic Si compounds represented by the above formula (1) or (3) are preferable as they exist in a liquid form at a room temperature, are capable of dissolving the organic Hf compounds, and have excellent volatilization stability, film forming rate, and step coverage.
The invention according to claim 8 is the raw material solution for metal organic chemical vapor deposition method according to claim 6, in which the organic Hf compound is represented by the following formula (4).
Hf(R4R5N)4 (4)
(wherein, R4 and R5 are alkyl groups having 1 or 2 carbon atoms, and R4 and R5 may be same or different from each other).
The invention according to claim 9 is the raw material solution for metal organic chemical vapor deposition method according to claim 6, in which the organic Hf compound is represented by the following formula (5)
Hf(OR6)4 (5)
(wherein, R6 is a straight or branched alkyl group having 1 to 4 carbon atoms).
The invention according to claim 8 or 9 is preferable as the organic Hf compound represented by the above-mentioned formula (4) or (5) easily dissolves in the organic Si compound, and has excellent volatilization stability, film forming rate, and step coverage.
The invention according to claim 10 is a method for manufacturing composite oxide film containing Hf-Si, which includes preparing the composite oxide film containing Hf-Si by using the raw material solution for metal organic chemical vapor deposition method according to any one of claims 6 to 9.
The invention according to claim 10 can form a film at a higher film forming rate by using the above-mentioned single solution of raw material solution for MOCVD method, in comparison with a conventional case where two solutions of raw material solutions for MOCVD method are respectively supplied to prepare a film, and further obtains the composite oxide film containing Hf-Si having a high adhesivity with the substrate.
The invention according to claim 11 is the method for manufacturing composite oxide film containing Hf-Si which includes the steps of growing a Si film on a surface of a substrate by thermally decomposing an organic Si compound having a same or different composition from the organic Si compound used for the raw material solution for metal organic chemical vapor deposition method according to any one of claims 6 to 9 together with a reducing gas; and forming a HfSiO film on a surface of the grown Si film by supplying the raw material solution for metal organic chemical vapor deposition method according to any one of claims 6 to 9 together with an oxidizing agent and performing the thermal decomposition.
The present invention according to claim 11 further improves adhesivity of HfSiO film with a substrate by forming the HfSiO film on a surface of the Si film grown in advance on a surface of the substrate.
The invention according to claim 12 is the method for manufacturing composite oxide film containing Hf-Si, which includes the steps of growing a Si film on a surface of a substrate by thermally decomposing the organic Si compound having a same or different composition from the organic Si compound used for the raw material solution for metal organic chemical vapor deposition method according to any one of claims 6 to 9 together with a reducing gas; and forming a HfSiON film on a surface of the grown Si film by supplying the raw material solution for metal organic chemical vapor deposition method according to any one of claims 6 to 9 together with an oxidizing agent and a nitrogen source and then performing the thermal decomposition.
The present invention according to claim 12 further improves adhesivity of HfSiON film with a substrate by forming the HfSiON film on a surface of the Si film grown in advance on a surface of the substrate.
Hereinafter, the invention will be described in detail with reference to suitable forms of embodiment.
The raw material solution for the MOCVD method according to the invention is a single solution of the metalorganic compound raw material for a film containing a plurality of metals such as the composite oxide film containing Hf-Si, and is obtained by mixing the organic Si compound with the organic Hf compound in a predetermined ratio and then dissolving the organic Hf compound in the organic Si compound.
The organic Si compound used for the raw material solution for the MOCVD method of the invention is represented by the following formula (1).
(R1R2N)aSiH(4-n) (1)
(wherein, R1 and R2 are straight or branched alkyl groups having 1 to 4 carbon atoms provided that R1 and R2 are same with each other, R1 is an alkyl group having 1 or 2 carbon atoms and R2 is a straight or branched alkyl group having 2 to 4 carbon atoms provided that R1 and R2 are different from each other, and n is an integer of 1 to 4).
Representative examples of the compound represented by the above formula (1) include Si[(CH3)2N]4, Si[(C2H5)2N]4, Si[(C3H7)2N]4 Si[(C4H9)2N]4, Si[(CH3)(C2H5)N]4, Si[(CH3)(C3H7)N]4, Si[(CH3)(C4H9)N]4, Si[(C2H5)(C3H7)N]4, Si[(C2H5)(C4H9)N]4, SiH[(CH3)2N]3, and the like. There is no doubt that other than these representative compounds, any other organic Si compound satisfying the above formula (1) can be used as the raw material solution of the invention. The organic Si compounds represented by the above formula (1) are preferable as they exist in a liquid form at a room temperature, capable of dissolving the organic Hf compounds represented by a formula (2) to be described later, and have excellent volatilization stability, film forming rate, and step coverage.
The organic Hf compound used for the MOCVD method of the invention is represented by the following formula (2).
Hf(OR3)4 (2)
(wherein, R3 is a straight or branched alkyl group having 1 to 4 carbon atoms).
A representative example of the compound represented by the above formula (2) includes Hf(t-C3H7O)4. There is no doubt that other than the representative compound, any other organic Hf compound satisfying the above formula (2) can be used as the raw material solution of the invention. The organic Hf compound represented by the above formula (2) is preferable as it easily dissolves in the above-mentioned organic Si compound represented by the formula (1), and has excellent volatilization stability, film forming rate, and step coverage.
By using the single solution of the raw material solution for the MOCVD method prepared in the above manner, high film forming rate is achieved, and also a fine composite oxide film containing Hf-Si having a high adhesivity is obtained. The reason is thought as follow. Since in the raw material solution of the invention, an intermediate of Hf-Si mixed metal polynuclear molecule formed with the organic Hf compound and the organic Si compound is thought to be included in the organic Si compound that holds most of the liquid mixture, this intermediate nucleates an initial film-forming core, and the composite oxide containing Hf-Si, which is formed by thermally decomposing vapor of the organic Si compound, organic Hf compound and the intermediates thereof and then reacting with an oxidizing agent, may start to deposit mainly from the initial film-forming core. In this way of depositing the composite oxide containing Hf-Si after nucleation of the initial film-forming core, high film forming rate is achieved. In addition, a fine film is formed as the film is formed mainly from the initial film-forming core. Furthermore, the composite oxide film containing Hf-Si having a high adhesivity is obtained as the initial film-forming core increases the adhesivity with the substrate.
A mixing ratio of the organic Si compound and the organic Hf compound is preferably within the range of 0.001 to 0.5 wt % in a weight ratio (organic Hf compound/organic Si compound). If it is less than a lower limit value, high quality of complex oxide membrane containing Hf-Si cannot be formed as a component ratio of the organic Hf compound is too small, and if it is more than an upper limit value, the intermediate of Hf-Si mixed metal polynuclear molecule hardly forms as the component ratio of the organic Hf compound is too large. The above-mentioned mixing ratio ranging from 0.001 to 0.5 wt % in a weight ratio (organic Hf compound/organic Si compound) is specifically preferable.
The raw material solution for the MOCVD method according to the invention is a single solution of the metalorganic compound raw material for a film containing a plurality of metals such as the composite oxide film containing Hf-Si. It is prepared as a single solution by mixing the organic Si compound with the organic Hf compound in the mixing ratio ranged from 0.001 to 0.5 wt % in a weight ratio (organic Hf compound/organic Si compound) and then by dissolving the organic Hf compound in the organic Si compound, and the solution is obtained by heating the mixed solution at 20 to 100° C. By using the single solution of the raw material solution for MOCVD method prepared in the above manner, high film forming rate is achieved, and also a fine composite oxide film containing Hf-Si having a high adhesivity is obtained. The reason is thought as follow. Since in the raw material solution of the invention, an intermediate of Hf-Si mixed metal polynuclear molecule, for example the intermediate represented by the following formula (6), formed with the organic Hf compound and the organic Si compound is thought to be included in the organic Si compound that holds most of the liquid mixture, this intermediate having a such structure nucleates the initial film-forming core, and the composite oxide containing Hf-Si, which is formed by thermally decomposing vapor of the organic Si compound, organic Hf compound and the intermediates thereof and then reacting with an oxidizing agent, may start to deposit mainly from the initial film-forming core. In this way of depositing the composite oxide containing Hf-Si after nucleation of the initial film-forming core, high film forming rate is achieved. In addition, a fine film is formed as the film is formed mainly from the initial film-forming core. Furthermore, the composite oxide film containing Hf-Si having a high adhesivity is obtained as the initial film-forming core increases the adhesivity with the substrate. Dotted lines shown in the formula (6) represent a weak bond.
An intermediate when using a compound including the organic Si compound and the organic Hf compound together with nitrogen is represented in the formula (6), but in a case where a compound including oxygen is used as any one or both of the organic Si compound and the organic Hf compound, it can be thought that a form of Hf-Si mixed metal polynuclear molecule having a structure resembling the intermediate shown in the above formula (6) is taken.
The mixing ratio of the organic Hf compound and the organic Si compound is provided to be within the above-mentioned range, because if it is less than the lower limit value, high quality of composite oxide film containing Hf-Si cannot be formed as the component ratio of the organic Hf compound is too small, and if it is more than the upper limit value, the intermediate of Hf-Si mixed metal polynuclear molecule hardly forms as the component ratio of the organic Hf compound is too large. The mixing ratio is more preferably within the range of 0.01 to 0.1 wt % in a weight ratio (organic Hf compound/organic Si compound). In addition, the organic Hf compound and the organic Si compound are mixed in a predetermined ratio and dissolved to be heat treated at the above-mentioned temperature range, so as to form the intermediate of Hf-Si mixed metal polynuclear molecule by stably attacking the organic Si compound to the organic Hf compound. Specifically preferable heating temperature to be applied to the solution is within the range of 20 to 100° C. Also, a heat period is preferably from 30 minutes to 1 hour.
The organic Si compound used for the raw material solution for MOCVD method of the invention is represented by each of following formulae (1) and (3).
(R1R2N)nSiH(4-n) (1)
(wherein, R1 and R2 are straight or branched alkyl groups having 1 to 4 carbon atoms provided that R1 and R2 are same with each other, R1 is an alkyl group having 1 or 2 carbon atoms and R2 is a straight or branched alkyl group having 2 to 4 carbon atoms provided that R1 and R2 are different from each other, and n is an integer of 1 to 4).
(R3O)mSiH(4-m) (3)
(wherein, R3 is a straight or branched alkyl group having 1 to 4 carbon atoms, and m is an integer of 1 to 4).
Representative examples of the compound represented by the above formula (1) include Si[(CH3)2N]4, Si[(C2H5)2N]4, Si[(C3H7)2N]4, Si[(C4H9)2N]4, Si[(CH3)(C2H5)N]4, Si[(CH3)(C3H7)N]4, Si[(CH3)(C4H9)N]4, Si[(C2H5)(C3H7)N]4, Si[(C2H5)(C4H9)N]4, SiH[(CH3)2N]3, and the like.
Representative examples of the compound represented by the above formula (3) include Si[(CH3)O]4, Si[(C2H5)O]4, Si[(C3H7)O]4, Si[(C4H9)O]4, SiH[(CH3)O]3, and the like. There is no doubt that other than these representative compounds, any other organic Si compound satisfying the above formulae (1) or (3) can be used as the raw material solution of the invention.
The organic Si compounds represented by each of the above formulae (1) or (3) are preferable as they exist in a liquid form at a room temperature, can dissolve the organic Hf compounds, and have excellent volatilization stability, film forming rate, and step coverage.
The organic Hf compound used for the raw material solution for MOCVD method of the invention is represented by each of following formulae (4) or (5).
Hf(R4R5N)4 (4)
(wherein, R4 and R5 are alkyl groups having 1 or 2 carbon atoms, and R4 and R5 may be same or different from each other).
Hf(OR6)4 (5)
(wherein, R6 is a straight or branched alkyl group having 1 to 4 carbon atoms).
Representative examples of the compound represented by the above formula (4) include Hf[(CH3)2N]4, Hf[(C2H5)2N]4, Hf[(CH3)(C2H5)N]4, and the like. A representative example of the compound represented by the above formula (5) includes Hf(t-C4H9O)4. There is no doubt that other these representative compounds, any other organic Hf compound satisfying the above formulae (4) or (5) can be used as the raw material solution of the invention.
The organic Hf compounds represented by the above formulae (4) or (5) are preferable as they easily dissolve in the organic Si compound, and have excellent volatilization stability, film forming rate, and step coverage.
Ligands coordinated to each of the organic Hf compound and the organic Si compound used for the raw material solution for MOCVD method of the invention may be a combination of ligands of same structure, but by using a combination of ligands of different structure, for example, the organic Si compound SiH[(CH3)2N]3 of which a dimethylamino group is coordinated to a Si atom and the organic Hf compound Hf[(C2H5)2N]4 of which a dimethylamino group is coordinated to a Hf atom, to prepare and use a single solution of raw material for MOCVD method, steric hindrance to the Hf-Si mixed metal polynuclear molecule formed as the intermediate is occurred. This occurrence of steric hindrance breaks symmetry of tetrahedral positions of the Hf element and Si element and thus it becomes easier to be dissolved. Therefore, nucleation of the initial film-forming core is promoted.
Next, the method for manufacturing composite oxide film containing Hf-Si of the invention will be described.
The method for manufacturing composite oxide film containing Hf-Si of the invention is characterized in that the composite oxide film containing Hf-Si is formed by using the raw material solution for MOCVD method of the invention described above. A film can be formed at a higher film forming rate by using the above-mentioned single solution of raw material solution for MOCVD method, in comparison with a case where each of two solutions of raw material solutions for MOCVD method are supplied to prepare a film. The reason for this is that the intermediate in the raw material solution supplied in the film forming chamber of an MOCVD apparatus is firstly thermally decomposed and nucleates the initial film-forming core which contributes in forming a film, and this initial film-forming core is modified on a surface of the substrate. Subsequently, vapor of the organic Si compound, the organic Hf compound, and the intermediates thereof thermally decompose and react with the oxidizing agent to produce HfSiO. When produced HfSiO gets closer to a heated substrate, HfSiO starts to deposit mainly from the initial film-forming core modified on a surface of the substrate, and thus it is considered that the film can be formed at a higher film forming rate in comparison with the conventional case where two solutions of raw material solution for MOCVD method are used. In addition, since the HfSiO deposits mainly from the initial film-forming core, obtained composite oxide film containing Hf-Si is compactly formed and thus has a high adhesitivity to the substrate.
The method for manufacturing composite oxide film containing Hf-Si of the invention will be described with reference to a method for forming a Hf-Si—O film.
As shown in
In this apparatus, a carrier gas consisting of an inert gas, e.g., N2, He, Ar, and the like is supplied from the carrier gas supplying pipe 21 into the raw material container 18 and the raw material solution for MOCVD method stored in the raw material container 18 is delivered via the feed pipe 22 to the vaporizer 26. The organic Si compound, organic Hf compound, and the intermediates thereof which have been vaporized by the vaporizer 26, is further fed via the piping 27 to the film forming chamber 10 by the carrier gas which is supplied from the carrier gas supplying pipe 28 into the vaporizer 26. The vapor of the organic Si compound, the organic Hf compound, and the intermediates thereof is thermally decomposed and reacted with the oxidizing agent supplied from the oxidizing agent supplying pipe 37 to form HfSiO, and the HfSiO formed is deposited on a surface of the substrate to form a Hf-Si—O film. Examples of the oxidizing agent include O2, H2O2, N2O, and the like.
In addition, as shown in
Other method for manufacturing composite oxide film containing Hf-Si of the invention will be described.
When a state leaving a substrate, for example a silicon substrate, in the air is kept, oxygen in the air reacts with Si on the substrate surface to naturally form an oxide film (SiO2) on a surface of the substrate. When the composite oxide film containing Hf-Si is formed on a surface having the naturally formed oxide film, a problem arises in that the inferior adhesivity of the composite oxide film containing Hf-Si occurs.
Therefore, in the other method for manufacturing composite oxide film containing Hf-Si of the invention, the organic Si compound is primarily thermally decomposed with a reducing gas to grow a Si film on a surface of the substrate. Specifically, the Si film is grown on a SiO2 surface formed on the Si substrate surface. A surface layer of the Si film grown on a surface of the substrate is thought to be in a Si—H structure, and it is assumed that this Si—H structure contributes to an adhesion improvement when forming the Hf-Si film containing composite oxide film in the process that will be continued after. The specific reason is thought as that when the Si—H grown on the surface of the substrate reacts with the initial film-forming core formed by thermally decomposing the intermediate in the raw material solution to easily modify the initial film-forming core on the surface of the substrate, and subsequently the formed HfSiO gets closer to the heated substrate, HfSiO starts to deposit mainly from the Si—H modified on the surface of the substrate and the initial film-forming core, and thus the HfSiO film having a high adhesivity is obtained. The organic Si compound used for growing the Si film may have same or different composition from the organic Si compound used for the raw material solution for MOCVD of the invention. Also, the reducing gas is preferably an H2 gas. A film thickness of the growing Si film is from about 0.1 to 10 nm, and preferably is 2 nm so as to observe its full effect.
Subsequently, the above-mentioned raw material solution for MOCVD method of the invention is supplied with the oxidizing agent and thermally decomposed to form the HfSiO film on a surface where the Si film is grown. As the oxidizing agent, O2, H2O2, N2O, and the like can be used. In this way of forming the HfSiO film on the surface of the Si film after growing the Si film on the surface of the substrate, interlayer of the Si substrate and the HfSiO film is stably formed.
Also, the above-mentioned raw material solution for MOCVD method of the invention is supplied together with the oxidizing agent and the nitrogen source and then thermally decomposed to form the HfSiON thin film. As the nitrogen source, N2 and NH3 are used.
Hereinafter, Examples of the invention will be described in details with reference to Comparative Examples.
Hf(t-C3H7O)4 and Si[(C2H5)2N]4 were prepared as the organic Hf compound and the organic Si compound, respectively. Next, the organic Hf compound and the organic Si compound were mixed at a room temperature in a ratio such that the weight ratio (organic Hf compound/organic Si compound) is 0.001 wt %, and the organic Hf compound was dissolved in the organic Si compound to prepare a single solution of the raw material solution for MOCVD method. Also, total of five raw material solutions for MOCVD method which differ in mixing ratio were prepared by respectively changing the mixing ratio of the organic Hf compound and the organic Si compound to 0.01 wt %, 0.1 wt %, 0.2 wt %, and 0.5 wt % in a weight ratio (organic Hf compound/organic Si compound).
Subsequently, Hf-Si—O thin films were formed respectively by using the prepared five raw material solutions for MOCVD method. In specific, at first, five silicon substrates having a SiO2 film (thickness of 5000 Å) on each surface were respectively prepared as substrates, and the substrates were installed in the film forming chamber of the MOCVD apparatus shown in
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example 1 except that the organic Si compound was changed to SiH[(CH3)2N]3, and the Hf-Si—O thin film was formed on a substrate in the same manner as in Example 1.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example 1 except that the organic Si compound was changed to Si[(CH3)2N]4, and the Hf-Si—O thin film was formed on a substrate in the same manner as in Example 1.
Hf(t-C3H7O)4 and Si[(C2H5)2N]4 were prepared as the organic Hf compound and the organic Si compound, respectively, and these organic Si compound and the organic Hf compound were respectively used as the raw material solutions for MOCVD method. That is, two solutions were used as the raw material solutions for MOCVD by individually preparing each solution of the organic Si compound and the organic Hf compound.
Subsequently, Hf-Si—O thin films were formed by using the prepared raw material solutions for MOCVD method. In specific, at first, five silicon substrates having a SiO2 film (thickness of 5000 Å) formed on each surface were respectively prepared as substrates, and the substrates were installed in the film forming chamber of the MOCVD apparatus shown in
<Comparative Test 1>
For each obtained Hf-Si—O thin film according to Examples 1 to 3 and Comparative Example 1, a film thickness test, and a peel test to examine adhesivity, per film formation time of the obtained Hf-Si—O thin film were carried out.
(1) A Film Thickness Test
The film thickness of the Hf-Si—O thin film on the film-formed substrate was determined from a cross-sectional scanning electron microscope image.
(2) A Peel Test
Each thin film formed on a flat portion of the film-formed substrate was subjected to following peel test. At first each thin film formed on a substrate was cut by using a cutter in a predetermined size to prepare 100 cut grids. Then, adhesive cellophane tape was adhered on the thin-film prepared in girds. The tape was peeled off from the thin film, and respectively examined the number peeled off by the tape and the number remained on the substrate among the thin film cut in 100 girds.
<Evaluation>
Obtained results of the film thickness and the peel test per film formation time are respectively shown in tables 1 and 2. The peel test shows the number of remaining substrates per 100 pieces of cut grid.
As clearly shown in the table 1, the films formed by using two raw material solutions according to Comparative Example 1 did not increase much in film thickness as time increases, and it was clear that the film formation is unstable. Correspondingly, the films formed by using the single solution according to Examples 1 to 3 had a significantly high film forming rate in comparison with Comparative Example 1, and stable film formation was obtained. In addition, according to the peel test, almost half of the grids were peeled off in the film formed by using the two raw material solutions according to Comparative Example 1, while most of the grids were remained on the substrate in films formed by using the single raw material solution according to Examples 1 to 3 and thus high adhesivity results were obtained.
Five raw material solutions for MOCVD method which differ in mixing ratio used in Example 1 were prepared to form a Hf-Si—O thin film. In specific, first, five silicon substrates having a SiO2 film (thickness of 5000 Å) on each surface were respectively prepared as substrates, and the substrates were installed in the film forming chamber of the MOCVD apparatus shown in
Two solutions used in Comparative Example 1 were prepared as the raw material solutions for MOCVD by individually preparing the organic Si compound and the organic Hf compound.
Subsequently, Hf-Si—O thin films were formed by using the prepared raw material solutions for MOCVD method. In specific, at first, five silicon substrates having a SiO2 film (thickness of 5000 Å) formed on each surface were respectively prepared as substrates, and the substrates were installed in the film forming chamber of the MOCVD apparatus shown in
Si[(C2H5)2N]4 was respectively fed as the organic Si compound at a rate of 0.1 g/min, and Si[(C2H5)2N]4 was thermally decomposed to grow the Si film on a surface of the substrate. Supply of the organic Si compound and the reducing gas was stopped when the film formation time reached 2 minutes. Next, O2 gas was used as a reactant gas and its partial pressure was set at 1000 ccm. Ar gas was used as a carrier gas, and individual raw material solutions of the organic Si compound and the organic Hf compound were respectively fed to form the Hf-Si—O thin film on a surface of the grown Si film. The substrates were taken out by one from the film forming chamber when the film formation time reached 1 minute, 2 minutes, 3 minutes, 4 minutes, and 5 minutes, respectively. Supplying ratio of the organic Si compound and the organic Hf compound raw material solutions during forming the film was changed to form a Hf-Si—O thin film having a same composition to the Hf-Si—O thin film formed by using the five raw material solutions for MOCVD method which differ in mixing ratio in Example 4.
<Comparative Test 2>
For each obtained Hf-Si—O thin film according to Example 4 and Comparative Example 2, a film thickness test, and a peel test to examine adhesivity, per film formation time of the obtained Hf-Si—O thin film were carried out in the same manner as in above-mentioned Comparative Test 1.
<Evaluation>
Obtained results of the film thickness and the peel test per film formation time are respectively shown in table 2. The peel test shows the number of remaining substrates per 100 pieces of cut grid.
As clearly shown in the table 2, the films formed by using two raw material solutions according to Comparative Example 2 did not increase much in film thickness as time increases, and it was clear that the film formation is unstable. Also, only the low values in the peel test were obtained meaning a result of some decrease in adhesivity. Correspondingly, the films formed by using the single solution according to Examples 4 had a significantly high film forming rate in comparison with Comparative Example 2, and stable film formation was obtained. Furthermore, films having excellent adhesivity were obtained.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example 1 to form Hf-Si—O thin films on substrates in the same manner as in Example 1, except that Si[(CH3)2N]4 was used as the organic Si compound, and Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example 1 to form Hf-Si—O thin films on substrates in the same manner as in Example 1, except that Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example 1 to form Hf-Si—O thin films on substrates in the same manner as in Example 1, except that Si[(n-C3H7)2N]4 was used as the organic Si compound, and Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example 1 to form Hf-Si—O thin films on substrates in the same manner as in Example 1, except that Si[(n-C4H9)2N]4 was used as the organic Si compound, and Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example 1 to form Hf-Si—O thin films on substrates in the same manner as in Example 1, except that Si[(CH3)(C2H5)N]4 was used as the organic Si compound, and Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example 1 to form Hf-Si—O thin films on substrates in the same manner as in Example 1, except that Si[(CH3)(n-C3H7)N]4 was used as the organic Si compound, and Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example 1 to form Hf-Si—O thin films on substrates in the same manner as in Example 1, except that Si[(CH3)(n-C4H9)N]4 was used as the organic Si compound, and Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example 1 to form Hf-Si—O thin films on substrates in the same manner as in Example 1, except that Si[(C2H5)(n-C3H7)N]4 was used as the organic Si compound, and Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example 1 to form Hf-Si—O thin films on substrates in the same manner as in Example 1, except that Si[(C2H5)(n-C4H9)N]4 was used as the organic Si compound, and Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
<Comparative Test 3>
For each obtained Hf-Si—O thin film according to Examples 5 to 40, a film thickness test, and a peel test to examine adhesivity, per film formation time of the obtained Hf-Si—O thin film were carried out in the same manner as in the above-mentioned Comparative Test 1.
<Evaluation>
Obtained results of the film thickness and the peel test per film formation time are respectively shown in tables 3 to 11. The peel test shows the number of remaining substrates per 100 pieces of cut grid.
As clearly shown in the tables 3 to 11, the films formed by using the single raw material solution according to Examples 5 to 40 had a significantly high film forming rate in comparison with Comparative Example 1, and stable film formation was obtained. Also, in the peel test, most of grids were remained on substrates in films formed by using the raw material solution according to Examples 5 to 40 and thus high adhesivity results were obtained.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example 1 so as to grow Si films on substrates and form Hf-Si—O thin films on surfaces of those Si films in the same manner as in Example 4, except that Si[(CH3)2N]4 was used as the organic Si compound, and Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example 1 so as to grow Si films on substrates and form Hf-Si—O thin films on surfaces of those Si films in the same manner as in Example 4, except that Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example 1 so as to grow Si films on substrates and form Hf-Si—O thin films on surfaces of those Si films in the same manner as in Example 4, except that Si[(n-C3H7)2N]4 was used as the organic Si compound, and Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example 1 so as to grow Si films on substrates and form Hf-Si—O thin films on surfaces of those Si films in the same manner as in Example 4, except that Si[(n-C4H9)2N]4 was used as the organic Si compound, and Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example 1 so as to grow Si films on substrates and form Hf-Si—O thin films on surfaces of those Si films in the same manner as in Example 4, except that Si[(CH3)(C2H5)N]4 was used as the organic Si compound, and Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example 1 so as to grow Si films on substrates and form Hf-Si—O thin films on surfaces of those Si films in the same manner as in Example 4, except that Si[(CH3)(n-C3H7)N]4 was used as the organic Si compound, and Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example 1 so as to grow Si films on substrates and form Hf-Si—O thin films on surfaces of those Si films in the same manner as in Example 4, except that Si[(CH3)(n-C4H9)N]4 was used as the organic Si compound, and Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example 1 so as to grow Si films on substrates and form Hf-Si—O thin films on surfaces of those Si films in the same manner as in Example 4, except that Si[(C2H5)(n-C3H7)N]4 was used as the organic Si compound, and Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example 1 so as to grow Si films on substrates and form Hf-Si—O thin films on surfaces of those Si films in the same manner as in Example 4, except that Si[(C2H5)(n-C4H9)N]4 was used as the organic Si compound, and Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
<Comparative Test 4>
For each obtained Hf-Si—O thin film according to Examples 41 to 76, a film thickness test, and a peel test to examine adhesivity, per film formation time of the obtained Hf-Si—O thin film were carried out in the same manner as in the above-mentioned Comparative Test 1.
<Evaluation>
Obtained results of the film thickness and the peel test per film formation time are respectively shown in tables 12 to 20. The peel test shows the number of remaining substrates per 100 pieces of cut grid.
As clearly shown in the tables 12 to 20, the HfSiO films formed by using the single raw material solution according to Examples 41 to 76 had a significantly high film forming rate in comparison with Comparative Example 2, and stable film formation was obtained. Also, in the peel test, most of grids were remained on substrates in HfSiO films formed by using the raw material solution according to Examples 41 to 76 and thus high adhesivity results were obtained.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example 1 so as to form Hf-Si—O—N thin films, except that Si[(CH3)2N]4 was used as the organic Si compound, and Hf(CH3O)4 was used as the organic Hf compound. In specific, first, five silicon substrates having a SiO2 film (thickness of 5000 Å) on each surface were respectively prepared as substrates, and the substrates were installed in the film forming chamber of the MOCVD apparatus shown in
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example 77 so as to grow Si films on substrates and form Hf-Si—O—N thin films on surfaces of those Si films in the same manner as in Example 77, except that Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example 77 so as to grow Si films on substrates and form Hf-Si—O—N thin films on surfaces of those Si films in the same manner as in Example 77, except that Si[(C2H5)2N]4 was used as the organic Si compound, and Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example 77 so as to grow Si films on substrates and form Hf-Si—O—N thin films on surfaces of those Si films in the same manner as in Example 77, except that Si[(n-C3H7)2N]4 was used as the organic Si compound, and Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example 77 so as to grow Si films on substrates and form Hf-Si—O—N thin films on surfaces of those Si films in the same manner as in Example 77, except that Si[(n-C4H9)2N]4 was used as the organic Si compound, and Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example 77 so as to grow Si films on substrates and form Hf-Si—O—N thin films on surfaces of those Si films in the same manner as in Example 77, except that Si[(CH3)(C2H5)N]4 was used as the organic Si compound, and Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example 77 so as to grow Si films on substrates and form Hf-Si—O—N thin films on surfaces of those Si films in the same manner as in Example 77, except that Si[(CH3)(n-C3H7)N]4 was used as the organic Si compound, and Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example 77 so as to grow Si films on substrates and form Hf-Si—O—N thin films on surfaces of those Si films in the same manner as in Example 77, except that Si[(CH3)(n-C4H9)N]4 was used as the organic Si compound, and Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example 77 so as to grow Si films on substrates and form Hf-Si—O—N thin films on surfaces of those Si films in the same manner as in Example 77, except that Si[(C2H5)(n-C3H7)N]4 was used as the organic Si compound, and Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example 77 so as to grow Si films on substrates and form Hf-Si—O—N thin films on surfaces of those Si films in the same manner as in Example 77, except that Si[(C2H5)(n-C4H9)N]4 was used as the organic Si compound, and Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
<Comparative Test 5>
For each obtained Hf-Si—O—N thin film according to Examples 77 to 112, a film thickness test, and a peel test to examine adhesivity, per film formation time of the obtained Hf-Si—O—N thin film were carried out in the same manner as in the above-mentioned Comparative Test 1.
<Evaluation>
Obtained results of the film thickness and the peel test per film formation time are respectively shown in tables 21 to 29. The peel test shows the number of remaining substrates per 100 pieces of cut grid.
As clearly shown in the tables 21 to 29, the HfSiON films formed by using the single raw material solution according to Examples 77 to 112 had a significantly high film forming rate and high film formation stability was obtained. Also, in the peel test, most of grids were remained on substrates in HfSiON films formed by using the raw material solution according to Examples 77 to 112 and thus high adhesivity results were obtained.
Hf[(C2H5)2N]4 and Si[(C2H5)2N]4 were prepared as the organic Hf compound and the organic Si compound, respectively. Next, the organic Hf compound and the organic Si compound were mixed at a room temperature in a ratio such that the weight ratio (organic Hf compound/organic Si compound) is 0.001 wt %, and the organic Hf compound was dissolved in the organic Si compound. This solution was then heated at a temperature of 60° C. for 2 hours to prepare a single solution of the raw material solution for MOCVD method. Also, total of five raw material solutions for MOCVD method which differ in mixing ratio were prepared by respectively changing the mixing ratio of the organic Hf compound and the organic Si compound to 0.01 wt %, 0.1 wt %, 0.2 wt %, and 0.5 wt % in a weight ratio (organic Hf compound/organic Si compound).
Subsequently, Hf-Si—O thin films were formed respectively by using the prepared five raw material solutions for MOCVD method. In specific, at first, five silicon substrates having a SiO2 film (thickness of 5000 Å) on each surface were respectively prepared as substrates, and the substrates were installed in the film forming chamber of the MOCVD apparatus shown in
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A1 except that the organic Si compound was changed to SiH[(CH3)2N]3, and the Hf-Si—O thin film was formed on a substrate in the same manner as in Example A1.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A1 except that the organic Si compound was changed to Si[(CH3)2N]4, and the Hf-Si—O thin film was formed on a substrate in the same manner as in Example A1.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A1 except that the organic Hf compound and the organic Si compound were changed to Hf[(CH3)2N]4 and Si[(CH3)2N]4, respectively, and the Hf-Si—O thin film was formed on a substrate in the same manner as in Example A1.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A1 except that the organic Hf compound and the organic Si compound were changed to Hf[(CH3)2N]4 and SiH[(CH3)2N]4, respectively, and the Hf-Si—O thin film was formed on a substrate in the same manner as in Example A1.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A1 except that the organic Hf compound and the organic Si compound were changed to Hf(t-C3H7O)4 and SiH[(CH3)2N]3, respectively, and the Hf-Si—O thin film was formed on a substrate in the same manner as in Example A1.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A1 except that the organic Hf compound was changed to Hf[(CH3)2N]4, and the Hf-Si—O thin film was formed on a substrate in the same manner as in Example A1.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A1 except that the organic Hf compound and the organic Si compound were changed to Hf(t-C3H7O)4 and Si[(CH3)2N]4, respectively, and the Hf-Si—O thin film was formed on a substrate in the same manner as in Example A1.
Two raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A1 except that the mixing ratios of the organic Hf compound and the organic Si compound were changed to 0.0005 wt % and 0.6 wt % in a weight ratio (organic Hf compound/organic Si compound), and the Hf-Si—O thin film was formed on a substrate in the same manner as in Example A1.
Hf[(C2H5)2N]4 and Si[(C2H5)2N]4 were prepared as the organic Hf compound and the organic Si compound, respectively, and these organic Si compound and the organic Hf compound were respectively used as the raw material solutions for MOCVD method. That is, two solutions were used as the raw material solutions for MOCVD by individually preparing each solution of the organic Si compound and the organic Hf compound.
Subsequently, Hf-Si—O thin films were formed by using the prepared raw material solutions for MOCVD method. In specific, at first, five silicon substrates having a SiO2 film (thickness of 5000 Å) formed on each surface were respectively prepared as substrates, and the substrates were installed in the film forming chamber of the MOCVD apparatus shown in
<Comparative Test A1>
For each obtained Hf-Si—O thin film according to Examples A1 to A8 and Comparative Examples A1 and A2, a film thickness test, and a peel test to examine adhesivity, per film formation time of the obtained Hf-Si—O thin film were carried out.
(1) A Film Thickness Test
The film thickness of the Hf-Si—O thin film on the film-formed substrate was determined from a cross-sectional scanning electron microscope image.
(2) A Peel Test
Each thin film formed on a flat portion of the film-formed substrate was subjected to following peel test. At first each thin film formed on a substrate was cut by using a cutter in a predetermined size to prepare 100 cut grids. Then, adhesive cellophane tape was adhered on the thin-film prepared in girds. The tape was peeled off from the thin film, and respectively examined the number peeled off by the tape and the number remained on the substrate among the thin film cut in 100 girds.
<Evaluation>
Obtained results of the film thickness and the peel test per film formation time are respectively shown in tables 30 and 31. The peel test shows the number of remaining substrates per 100 pieces of cut grid. In the tables 30 and 31, letter ‘A’s numbering Examples and Comparative Examples are omitted.
As clearly shown in the tables 30 and 31, the films formed by using the raw material solution mixed in a ratio outside the range of the invention according to Comparative Example A1 were low in adhesivity and film forming rate. In addition, the films formed by using two raw material solutions according to Comparative Example A2 did not increase much in film thickness as time increases, and it was clear that the film formation is unstable.
Correspondingly, the films formed by using the single solution according to Examples A1 to A8 had a significantly high film forming rate in comparison with Comparative Examples A1 and A2, and highly stable film formation was obtained. Furthermore, according to the peel test, almost half of the grids were peeled off in the films formed by using the raw material solution mixed in a ratio outside the range of the invention according to Comparative Example 1 and the films formed by using the two raw material solutions according to Comparative Example 2, while most of the grids were remained on the substrate in films formed by using the single raw material solution according to Examples 1 to 8 and thus high adhesivity results were obtained.
Five raw material solutions for MOCVD method which differ in mixing ratio used in Example A1 were prepared to form a Hf-Si—O thin film. In specific, first, five silicon substrates having a SiO2 film (thickness of 5000 Å) on each surface were respectively prepared as substrates, and the substrates were installed in the film forming chamber of the MOCVD apparatus shown in
Two raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A9 except that the mixing ratios of the organic Hf compound and the organic Si compound were changed to 0.0005 wt % and 0.6 wt % in a weight ratio (organic Hf compound/organic Si compound), and the Hf-Si—O thin film was formed on a substrate in the same manner as in Example 13.
Two solutions used in Comparative Example A2 were prepared as the raw material solutions for MOCVD by individually preparing the organic Si compound and the organic Hf compound.
Subsequently, Hf-Si—O thin films were formed by using the prepared raw material solutions for MOCVD method. In specific, at first, five silicon substrates having a SiO2 film (thickness of 5000 Å) formed on each surface were respectively prepared as substrates, and the substrates were installed in the film forming chamber of the MOCVD apparatus shown in
<Comparative Test A2>
For each obtained Hf-Si—O thin film according to Example A9 and Comparative Example A3 and A4, a film thickness test, and a peel test to examine adhesivity, per film formation time of the obtained Hf-Si—O thin film were carried out in the same manner as in above-mentioned Comparative Test A1.
<Evaluation>
Obtained results of the film thickness and the peel test per film formation time are respectively shown in table 32. The peel test shows the number of remaining substrates per 100 pieces of cut grid. In the table 32, letter ‘A’s numbering Examples and Comparative Examples are omitted.
As clearly shown in the table 32, the films formed by using the raw material solution mixed in a ratio outside the range of the invention according to Comparative Example A3 were low in adhesivity and film forming rate. In addition, the films formed by using two raw material solutions according to Comparative Example A4 did not increase much in film thickness as time increases, and it was clear that the film formation is unstable. Also, only the low values in the peel test were obtained meaning a result of some decrease in adhesivity. Correspondingly, the films formed by using the single solution according to Example 13 had a significantly high film forming rate in comparison with Comparative Examples A3 and A4, and stable film formation was obtained. Furthermore, films having excellent adhesivity were obtained.
Hf[(C2H5)2N]4 and Si[(C2H5)O]4 were prepared as the organic Hf compound and the organic Si compound, respectively. Next, the organic Hf compound and the organic Si compound were mixed at a room temperature in a ratio such that the weight ratio (organic Hf compound/organic Si compound) is 0.001 wt %, and the organic Hf compound was dissolved in the organic Si compound. This solution was then heated at a temperature of 60° C. for 1 hour to prepare a single solution of the raw material solution for MOCVD method. Also, total of five raw material solutions for MOCVD method which differ in mixing ratio were prepared by respectively changing the mixing ratio of the organic Hf compound and the organic Si compound to 0.01 wt %, 0.1 wt %, 0.2 wt %, and 0.5 wt % in a weight ratio (organic Hf compound/organic Si compound).
Subsequently, Hf-Si—O thin films were respectively formed on substrates by using the prepared five raw material solutions for MOCVD method in the same manner as in Example A1.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A10 to form Hf-Si—O thin films on substrates in the same manner as in Example A1, except that Hf[(CH3)2N]4 was used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A10 to form Hf-Si—O thin films on substrates in the same manner as in Example A1, except that Hf[(CH3)(C2H5)N]4 was used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A10 to form Hf-Si—O thin films on substrates in the same manner as in Example A1, except that Hf(t-C3H7O)4 was used as the organic Hf compound.
<Comparative Test A3>
For each obtained Hf-Si—O thin film according to Examples A10 to A13, a film thickness test, and a peel test to examine adhesivity, per film formation time of the obtained Hf-Si—O thin film were carried out in the same manner as in the above-mentioned Comparative Test A1.
<Evaluation>
Obtained results of the film thickness and the peel test per film formation time are respectively shown in table 33. The peel test shows the number of remaining substrates per 100 pieces of cut grid. In the table 33, letter ‘A’s numbering Examples are omitted.
As clearly shown in the table 33, the films formed by using the single raw material solution according to Examples A10 to 13 had a significantly high film forming rate and stable film formation was obtained. Furthermore, films having excellent adhesivity were obtained.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A1 to form Hf-Si—O thin films on substrates in the same manner as in Example A1, except that Si[(CH3)2N]4 was used as the organic Si compound, and Hf[(CH3)(C2H5)N]4, Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A1 to form Hf-Si—O thin films on substrates in the same manner as in Example A1, except that Si[(C2H5)2N]4 was used as the organic Si compound, and Hf[(CH3)(C2H5)N]4, Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A1 to form Hf-Si—O thin films on substrates in the same manner as in Example A1, except that Si[(n-C3H7)2N]4 was used as the organic Si compound, and Hf[(CH3)2N]4, Hf[(C2H5)2N]4, Hf[(CH3)(C2H5)N]4, Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A1 to form Hf-Si—O thin films on substrates in the same manner as in Example A1, except that Si[(n-C4H9)2N]4 was used as the organic Si compound, and Hf[(CH3)2N]4, Hf[(C2H5)2N]4, Hf[(CH3)(C2H5)N]4, Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A1 to form Hf-Si—O thin films on substrates in the same manner as in Example A1, except that Si[(CH3)(C2H5)N]4 was used as the organic Si compound, and Hf[(CH3)2N]4, Hf[(C2H5)2N]4, Hf[(CH3)(C2H5)N]4, Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A1 to form Hf-Si—O thin films on substrates in the same manner as in Example A1, except that Si[(CH3)(n-C3H7)N]4 was used as the organic Si compound, and Hf[(CH3)2N]4, Hf[(C2H5)2N]4, Hf[(CH3)(C2H5)N]4, Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A1 to form Hf-Si—O thin films on substrates in the same manner as in Example A1, except that Si[(CH3)(n-C4H9)N]4 was used as the organic Si compound, and Hf[(CH3)2N]4, Hf[(C2H5)2N]4, Hf[(CH3)(C2H5)N]4, Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A1 to form Hf-Si—O thin films on substrates in the same manner as in Example A1, except that Si[(C2H5)(n-C3H7)N]4 was used as the organic Si compound, and Hf[(CH3)2N]4, Hf[(C2H5)2N]4, Hf[(CH3)(C2H5)N]4, Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A1 to form Hf-Si—O thin films on substrates in the same manner as in Example A1, except that Si[(C2H5)(n-C4H9)N]4 was used as the organic Si compound, and Hf[(CH3)2N]4, Hf[(C2H5)2N]4, Hf[(CH3)(C2H5)N]4, Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A1 to form Hf-Si—O thin films on substrates in the same manner as in Example A1, except that Si(CH3O)4 was used as the organic Si compound, and Hf[(CH3)2N]4, Hf[(C2H5)2N]4, Hf[(CH3)(C2H5)N]4, Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A1 to form Hf-Si—O thin films on substrates in the same manner as in Example A1, except that Si(C2H5O)4 was used as the organic Si compound, and Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A1 to form Hf-Si—O thin films on substrates in the same manner as in Example A1, except that Si(n-C3H7O)4 was used as the organic Si compound, and Hf[(CH3)2N]4, Hf[(C2H5)2N]4, Hf[(CH3)(C2H5)N]4, Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A1 to form Hf-Si—O thin films on substrates in the same manner as in Example A1, except that Si(n-C4H9O)4 was used as the organic Si compound, and Hf[(CH3)2N]4, Hf[(C2H5)2N]4, Hf[(CH3)(C2H5)N]4, Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
<Comparative Test A4>
For each obtained Hf-Si—O thin film according to Examples A14 to A97, a film thickness test, and a peel test to examine adhesivity, per film formation time of the obtained Hf-Si—O thin film were carried out in the same manner as in the above-mentioned Comparative Test A1.
<Evaluation>
Obtained results of the film thickness and the peel test per film formation time are respectively shown in tables 34 to 50. The peel test shows the number of remaining substrates per 100 pieces of cut grid. In the tables 34 to 50, letter ‘A’s numbering Examples are omitted.
As clearly shown in the tables 34 to 50, the films formed by using the single raw material solution according to Examples A14 to A97 had a significantly high film forming rate in comparison with Comparative Example 1, and stable film formation was obtained.
Also, in the peel test, most of grids were remained on substrates in films formed by using the raw material solution according to Examples A14 to A97 and thus high adhesivity results were obtained.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A1 so as to grow Si films on substrates and form Hf-Si—O thin films on surfaces of those Si films in the same manner as in Example A9, except that Si[(CH3)2N]4 was used as the organic Si compound, and Hf[(CH3)2N]4, Hf[(C2H5)2N]4, Hf[(CH3)(C2H5)N]4, Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O) 4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A1 so as to grow Si films on substrates and form Hf-Si—O thin films on surfaces of those Si films in the same manner as in Example A9, except that Hf[(CH3)2N]4, Hf[(CH3)(C2H5)N]4, Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A1 so as to grow Si films on substrates and form Hf-Si—O thin films on surfaces of those Si films in the same manner as in Example A9, except that Si[(n-C3H7)2N]4 was used as the organic Si compound, and Hf[(CH3)2N]4, Hf[(C2H5)2N]4, Hf[(CH3)(C2H5)N]4, Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A1 so as to grow Si films on substrates and form Hf-Si—O thin films on surfaces of those Si films in the same manner as in Example A9, except that Si[(n-C4H9)2N]4 was used as the organic Si compound, and Hf[(CH3)2N]4, Hf[(C2H5)2N]4, Hf[(CH3)(C2H5)N]4, Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O) 4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A1 so as to grow Si films on substrates and form Hf-Si—O thin films on surfaces of those Si films in the same manner as in Example A9, except that Si[(CH3)(C2H5)N]4 was used as the organic Si compound, and Hf[(CH3)2N]4, Hf[(C2H5)2N]4, Hf[(CH3)(C2H5)N]4, Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A1 so as to grow Si films on substrates and form Hf-Si—O thin films on surfaces of those Si films in the same manner as in Example A9, except that Si[(CH3)(n-C3H7)N]4 was used as the organic Si compound, and Hf[(CH3)2N]4, Hf[(C2H5)2N]4, Hf[(CH3)(C2H5)N]4, Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A1 so as to grow Si films on substrates and form Hf-Si—O thin films on surfaces of those Si films in the same manner as in Example A9, except that Si[(CH3)(n-C4H9)N]4 was used as the organic Si compound, and Hf[(CH3)2N]4, Hf[(C2H5)2N]4, Hf[(CH3)(C2H5)N]4, Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A1 so as to grow Si films on substrates and form Hf-Si—O thin films on surfaces of those Si films in the same manner as in Example A9, except that Si[(C2H5)(n-C3H7)N]4 was used as the organic Si compound, and Hf[(CH3)2N]4, Hf[(C2H5)2N]4, Hf[(CH3)(C2H5)N]4, Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A1 so as to grow Si films on substrates and form Hf-Si—O thin films on surfaces of those Si films in the same manner as in Example A9, except that Si[(C2H5)(n-C4H9)N]4 was used as the organic Si compound, and Hf[(CH3)2N]4, Hf[(C2H5)2N]4, Hf[(CH3)(C2H5)N]4, Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example 1 so as to grow Si films on substrates and form Hf-Si—O thin films on surfaces of those Si films in the same manner as in Example 9, except that Si(CH3O)4 was used as the organic Si compound, and Hf[(CH3)2N]4, Hf[(C2H5)2N]4, Hf[(CH3)(C2H5)N]4, Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O) 4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A1 so as to grow Si films on substrates and form Hf-Si—O thin films on surfaces of those Si films in the same manner as in Example A9, except that Si(C2H5O)4 was used as the organic Si compound, and Hf[(CH3)2N]4, Hf[(C2H5)2N]4, Hf[(CH3)(C2H5)N]4, Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O) 4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A1 so as to grow Si films on substrates and form Hf-Si—O thin films on surfaces of those Si films in the same manner as in Example A9, except that Si (n-C3H7O)4 was used as the organic Si compound, and Hf[(CH3)2N]4, Hf[(C2H5)2N]4, Hf[(CH3)(C2H5)N]4, Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O) 4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A1 so as to grow Si films on substrates and form Hf-Si—O thin films on surfaces of those Si films in the same manner as in Example A9, except that Si (n-C4H9O) 4 was used as the organic Si compound, and Hf[(CH3)2N]4, Hf[(C2H5)2N]4, Hf[(CH3)(C2H5)N]4, Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
<Comparative Test A5>
For each obtained Hf-Si—O thin film according to Examples A98 to A187, a film thickness test, and a peel test to examine adhesivity, per film formation time of the obtained Hf-Si—O thin film were carried out in the same manner as in the above-mentioned Comparative Test A1.
<Evaluation>
Obtained results of the film thickness and the peel test per film formation time are respectively shown in tables 51 to 68. The peel test shows the number of remaining substrates per 100 pieces of cut grid. In the tables 51 to 68, letter ‘A’s numbering Examples are omitted.
As clearly shown in the tables 51 to 68, the HfSiO films formed by using the single raw material solution according to Examples A98 to A187 had a significantly high film forming rate in comparison with Comparative Example 2, and stable film formation was obtained. Also, in the peel test, most of grids were remained on substrates in HfSiO films formed by using the raw material solution according to Examples A98 to A187 and thus high adhesivity results were obtained.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example 1 to form Hf-Si—O—N thin films on substrates, except that Si[(CH3)2N]4 was used as the organic Si compound, and Hf[(CH3)2N]4 was used as the organic Hf compound. In specific, first, five silicon substrates having a SiO2 film (thickness of 5000 Å) on each surface were respectively prepared as substrates, and the substrates were installed in the film forming chamber of the MOCVD apparatus shown in
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A188 so as to grow Si films on substrates and form Hf-Si—O—N thin films on surfaces of those Si films in the same manner as in Example A188, except that Hf[(C2H5)2N]4, Hf[(CH3)(C2H5)N]4, Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A188 so as to grow Si films on substrates and form Hf-Si—O—N thin films on surfaces of those Si films in the same manner as in Example A188, except that Si[(C2H5)2N]4 was used as the organic Si compound, and Hf[(CH3)2N]4, Hf[(C2H5)2N]4, Hf[(CH3)(C2H5)N]4, Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A188 so as to grow Si films on substrates and form Hf-Si—O—N thin films on surfaces of those Si films in the same manner as in Example A188, except that Si[(n-C3H7)2N]4 was used as the organic Si compound, and Hf[(CH3)2N]4, Hf[(C2H5)2N]4, Hf[(CH3)(C2H5)N]4, Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A188 so as to grow Si films on substrates and form Hf-Si—O—N thin films on surfaces of those Si films in the same manner as in Example A188, except that Si[(n-C4H9)2N]4 was used as the organic Si compound, and Hf[(CH3)2N]4, Hf[(C2H5)2N]4, Hf[(CH3)(C2H5)N]4, Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A188 so as to grow Si films on substrates and form Hf-Si—O—N thin films on surfaces of those Si films in the same manner as in Example A188, except that Si[(CH3)(C2H5)N]4 was used as the organic Si compound, and Hf[(CH3)2N]4, Hf[(C2H5)2N]4, Hf[(CH3)(C2H5)N]4, Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A188 so as to grow Si films on substrates and form Hf-Si—O—N thin films on surfaces of those Si films in the same manner as in Example A188, except that Si[(CH3)(n-C3H7)N]4 was used as the organic Si compound, and Hf[(CH3)2N]4, Hf[(C2H5)2N]4, Hf[(CH3)(C2H5)N]4, Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A188 so as to grow Si films on substrates and form Hf-Si—O—N thin films on surfaces of those Si films in the same manner as in Example A188, except that Si[(CH3)(n-C4H9)N]4 was used as the organic Si compound, and Hf[(CH3)2N]4, Hf[(C2H5)2N]4, Hf[(CH3)(C2H5)N]4, Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A188 so as to grow Si films on substrates and form Hf-Si—O—N thin films on surfaces of those Si films in the same manner as in Example A188, except that Si[(C2H5)(n-C3H7)N]4 was used as the organic Si compound, and Hf[(CH3)2N]4, Hf[(C2H5)2N]4, Hf[(CH3)(C2H5)N]4, Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A188 so as to grow Si films on substrates and form Hf-Si—O—N thin films on surfaces of those Si films in the same manner as in Example A188, except that Si[(C2H5)(n-C4H9)N]4 was used as the organic Si compound, and Hf[(CH3)2N]4, Hf[(C2H5)2N]4, Hf[(CH3)(C2H5)N]4, Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A188 so as to grow Si films on substrates and form Hf-Si—O—N thin films on surfaces of those Si films in the same manner as in Example A188, except that Si(CH3O)4 was used as the organic Si compound, and Hf[(CH3)2N]4, Hf[(C2H5)2N]4, Hf[(CH3)(C2H5)N]4, Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A188 so as to grow Si films on substrates and form Hf-Si—O—N thin films on surfaces of those Si films in the same manner as in Example A188, except that Si(C2H5O)4 was used as the organic Si compound, and Hf[(CH3)2N]4, Hf[(C2H5)2N]4, Hf[(CH3)(C2H5)N]4, Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A188 so as to grow Si films on substrates and form Hf-Si—O—N thin films on surfaces of those Si films in the same manner as in Example A188, except that Si(n-C3H7O)4 was used as the organic Si compound, and Hf[(CH3)2N]4, Hf[(C2H5)2N]4, Hf[(CH3)(C2H5)N]4, Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
Five raw material solutions for MOCVD method which differ in mixing ratio were respectively prepared in the same manner as in Example A188 so as to grow Si films on substrates and form Hf-Si—O—N thin films on surfaces of those Si films in the same manner as in Example A188, except that Si(n-C4H9O)4 was used as the organic Si compound, and Hf[(CH3)2N]4, Hf[(C2H5)2N]4, Hf[(CH3)(C2H5)N]4, Hf(CH3O)4, Hf(C2H5O)4, Hf(n-C3H7O)4 and Hf(n-C4H9O)4 were used as the organic Hf compound.
<Comparative Test A6>
For each obtained Hf-Si—O—N thin film according to Examples A188 to A278, a film thickness test, and a peel test to examine adhesivity, per film formation time of the obtained Hf-Si—O—N thin film were carried out in the same manner as in the above-mentioned Comparative Test A1.
<Evaluation>
Obtained results of the film thickness and the peel test per film formation time are respectively shown in tables 69 to 87. The peel test shows the number of remaining substrates per 100 pieces of cut grid. In the tables 69 to 87, letter ‘A’s numbering Examples are omitted.
As clearly shown in the tables 69 to 87, the HfSiON films formed by using the single raw material solution according to Examples A188 to A278 had a significantly high film forming rate, and stable film formation was obtained. Also, in the peel test, most of grids were remained on substrates in HfSiON films formed by using the raw material solution according to Examples A188 to A278 and thus high adhesivity results were obtained.
The raw material solution for MOCVD method of the invention is a single solution of the metalorganic compound raw material for a film containing a plurality of metals such as the composite oxide film containing Hf-Si. This raw material solution is prepared as a single solution by mixing the organic Si compound with the organic Hf compound in a predetermined mixing ratio and then by dissolving the organic Hf compound in the organic Si compound, and the solution is obtained by heating in a predetermined temperature range to be prepared. Since the single solution of the raw material solution for MOCVD method prepared in such manner is thought to include an intermediate of Hf-Si mixed metal polynuclear molecule formed with the organic Hf compound and the organic Si compound, this intermediate nucleates the initial film-forming core on a surface of the substrate. Therefore, high film forming rate is obtained by using the raw material solution of the invention.
In addition, the method for manufacturing composite oxide film containing Hf-Si is a method for manufacturing composite oxide film containing Hf-Si by using the above-mentioned raw material solution for MOCVD method. By using the above-mentioned single raw material solution for MOCVD method of the invention, films can be formed at a higher film forming rate in comparison with the conventional case where two solutions of raw material solution for MOCVD method are respectively supplied to form a film. Further, obtained composite oxide film containing Hf-Si has a high adhesivity with a substrate.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2004-255097 | Sep 2004 | JP | national |
| 2004-255098 | Sep 2004 | JP | national |
| 2005-250917 | Aug 2005 | JP | national |
| 2005-250945 | Aug 2005 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP05/16082 | 9/2/2005 | WO | 00 | 10/16/2007 |
