This application is based upon and claims the benefit of priority from the prior Japanese Patent Application No. 2009-283006, filed on Dec. 14, 2009, the entire contents of which are incorporated herein by reference.
Embodiments described herein relate generally to a semiconductor device, more specifically, to a semiconductor device having a ferroelectric capacitor and a manufacturing method thereof.
FeRAM (ferroelectric random access memory) which is a memory using a capacitor, for example, a nonvolatile memory using a ferroelectric thin film, replaces the capacitor portion of a DRAM with a ferroelectric capacitor. The FeRAM has the following features and is expected as a next-generation memory.
The FeRAM having the above advantages uses a ferroelectric thin film, such as PZT(Pb(ZrxTi1-x)O3), BIT(Bi4Ti3O12), and SBT(SrBi2Ta2O9), for the capacitor portion. Any of the materials also has a crystalline structure called a perovskite structure with an oxygen octahedron as a basic structure. In the perovskite structure, a metal atom A is arranged at each vertex (A site) of a cubic crystal system, an oxygen atom O is arranged at each face center thereof, and a metal atom B is arranged at a body center (B site) thereof.
Unlike a silicon oxide film which has conventionally been used as an insulating film, these materials do not exhibit ferroelectricity which is the feature of these materials in an amorphous state. This is because polarization of a ferroelectric substance such as PZT occurs as displacement of the charge centers of negative ions and positive ions has two metastable conditions and the metastable conditions occur by crystallization.
Accordingly, to obtain a ferroelectric capacitor having excellent characteristics, it is necessary to form a ferroelectric film having excellent crystallinity. In other words, to use the above material as a ferroelectric substance, a crystallization process (for example, crystallization thermal treatment at high temperature (annealing) or in-situ crystallization process at high temperature) is necessary. Depending on material, temperatures requirement for crystallization are typically at least 400° C. to 700° C.
Various ferroelectric film forming methods, such as a laser ablation method, a vacuum evaporation method, and an MBE method, have been studied. As those which are in practical use, there are a CVD (chemical vapor deposition) method, the sputtering method, and a CSD (chemical solution deposition) method.
The ferroelectric material actually used in the FeRAM is PZT or SBT. PZT has been studied for a thin film forming method from early on, also with many research examples using the CVD method, the sputtering method, and a sol-gel method, and is the first material to be made practical as a FeRAM.
Hereinafter, taking PZT as a representative ferroelectric material as an example, its features will be described. PZT has the following advantages.
As described above, as the crystallization temperature of PZT is about 600° C., in order to obtain a crystallized PZT film, it is necessary to form a film at 600° C. or higher, or to perform a thermal treatment at 600° C. or higher after film forming.
Of the PZT film forming methods, the sputtering method has been practically used most often. There are mainly two methods using the sputtering method. One is a method performing high-temperature film formation enabling in-situ crystallization. The other is a method performing annealing for crystallization after film deposition at room temperature.
When the former high-temperature film deposition is performed, as Pb has high volatility, it is desorbed from the inside of the formed PZT film and the target PZT. Therefore, there is a problem in composition controllability. Further, to prevent Pb desorption at the time of the high-temperature film deposition, it is also considered to use a multi-target sputtering device. However, as the distance between a target and a substrate is long, the film deposition speed is decreased, resulting in decrease of productivity.
In the case of the latter method performing annealing after film deposition, as Pb is desorbed at the time of annealing, a PZT film having an increased Pb composition is previously formed so as to obtain a proper Pb composition after annealing. This provides the PZT film excellent crystallinity. However, when a thick PZT film is formed, the control of the Pb composition becomes difficult so that stable film forming cannot be performed. In other words, the Pb composition of the PZT film is changed with time to perform sputtering. In addition, as a void due to Pb desorption occurs at the time of annealing, the film density of the PZT film is lowered. When a point defect is caused by Pb desorption, a fixed charge is created in the PZT film, resulting in deteriorated electric characteristic.
As another PZT film forming method, there is the CVD method. According to the CVD method, a PZT film having a desired Pb composition can be formed at a film forming temperature higher than the crystallization temperature (600° C.) by controlling the amount of supply of a source material. In other words, in the case of the CVD method, composition control is easy. Further, Pb desorption from the PZT film can also be prevented by controlling Pb partial pressure.
However, there are the following problems as the disadvantages of the CVD method. First, as an oxidation source (e.g., O2) is used, the surface of an Ir film (lower electrode) as the underlayer of the PZT film is oxidized to be IrOx. When the Ir film is oxidized in this manner, the amount of read signal from the FeRAM cell is reduced. This is because although the deposition of the PZT film with (111) orientation using the (111) orientation of Ir as a crystalline nucleus is desirable from the viewpoint of obtaining excellent characteristics, it becomes difficult when the Ir film is oxidized.
Second, there is a problem that crystallization is impeded by taking in carbon (C) or the like included in the source material as impurities in the PZT film. However, a method avoiding this problem by forming a PZT film at two stages has been known. In other words, first, at an early stage deposition for the PZT film, crystallization is promoted by lowering the O2 partial pressure and increasing the Pb concentration to form the PZT thin film (a thickness of about several nm). Thereafter, the PZT thick film of stoichiometry is formed over the PZT thin film under the conditions of the high O2 partial pressure. The thick PZT film can prevent void occurrence and is excellent in electric characteristic. However, when the PZT film forming by the two-stage CVD method is performed, so-called memory effect in which the previous film forming conditions change the following film deposition conditions occurs at the time of changing the concentration of a source gas during the PZT film deposition, resulting in deterioration of reproductivity of the PZT film.
As described above, according to the sputtering method, the PZT film which reduces impurities and is excellent in crystallinity can be formed, and the oxidation of the lower electrode of the capacitor can be prevented. However, there is a problem that Pb is desorbed and a void occurs due to the thermal treatment after film deposition. On the other hand, according to the CVD method, composition control is relatively easy, Pb desorption can be prevented, and the film forming rate is also high. However, as the lower electrode is oxidized, the PZT film which has excellent characteristics and in (111) orientation is hard to be formed.
Accordingly, the following manufacturing method of a ferroelectric capacitor of an FeRAM is disclosed in Japanese Patent Application Laid-open Publication No. 2008-124329. In this method, first, a PZT thin film is formed as a seed layer by the sputtering method, and then, a PZT film (bulk layer) is formed on the PZT film as the seed layer by the CVD method. As the sputtering method is used for forming the seed layer, the oxidation of the lower electrode can be prevented and the PZT film excellent in crystallinity can be formed. Then, as the CVD method is used for forming the PZT film as the bulk layer, the film deposition rate is high and composition controllability is excellent. However, as the conductive film (such as the Pt film and the Ir film) as the lower electrode and the PZT film have different crystalline structures, the PZT film having sufficient crystallinity cannot be obtained.
According to an embodiment, there is provided a method for manufacturing a semiconductor device having a ferroelectric capacitor including a lower electrode, an upper electrode, and a dielectric film provided between the lower electrode and the upper electrode. The method includes firstly forming a conductive film on the lower electrode. Next, it includes forming an SRO film on the conductive film. Then, it includes performing a first thermal treatment crystallizing the SRO film. Then, it includes forming a first PZT film on the SRO film by the sputtering method and performing a second thermal treatment crystallizing the first PZT film. Then, it includes forming the second PZT film on the first PZT film by the CVD method.
Hereinafter, a semiconductor device and a manufacturing method thereof according to an embodiment of the present invention will be described with reference to the drawings. Structure elements having the similar function in the respective drawings are indicated by same reference numerals and the detailed description will not be repeated.
A COP (capacitor on plug) type FeRAM manufacturing method according to this embodiment will be described with reference to
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(2) Next, a transistor (MOSFET) for performing a switch operation is manufactured in the transistor active region.
(2-1) A silicon oxide film 102 having a thickness of, e.g., about 60 Å, is formed on the entire surface of the p-type silicon substrate 100 by the thermal oxidation method. The silicon oxide film 102 is a gate insulating film of the MOSFET.
(2-2) An n+ type polycrystal silicon film 103 into which arsenic (As) is doped is formed on the silicon oxide film 102. Further, a WSix film 104 and a silicon nitride film (SiN) 105 are successively formed on the polycrystal silicon film 103.
(2-3) A stacking film including the silicon oxide film 102, the polycrystal silicon film 103, the WSix film 104, and the silicon nitride film 105 is processed by the typically used optical lithography method and RIE method to form gate stack.
(2-4) After a silicon nitride film is stacked over the gate stack and the p-type silicon substrate 100, side wall insulating films (spacer portions) 106 are formed on the side walls of the gate stack by the side wall leaving method with the RIE.
(2-5) Thereafter, although the description of the detailed process will be skipped, source-drain regions 107 are formed by the known ion implantation method and thermal treatment.
A MOSFET 10 is completed by the above process.
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(12) The RTA (rapid thermal annealing) is performed in an oxygen atmosphere to crystallize the SRO film 119.
At the time of the RTA, Ti atoms of the conductive film 118 are diffused into the SRO film 119 to promote the crystallization of the SRO film 119 so that the SRO film 119 can be sufficiently crystallized. The RTA is performed under the conditions of e.g., 550° C. and 30 seconds so that the SRO film 119 excellent in crystallinity can be easily formed. The crystallinity of the SRO film as an underlayer is improved in this manner so that the crystallinity of a below-described seed PZT film 120 can also be improved.
The reason why the crystallinity of the SRO is improved by the diffusion of the Ti atoms can be considered as follows. The Ti atoms diffused by the RTA substitute for Ru atoms arranged at the B site of the SRO having the perovskite structure. The Ti atoms which have substituted for the Ru atoms attract O atoms located in the face center of the perovskite crystalline structure. This can be considered to promote the crystallization of the SRO film.
Here, the thickness of the SRO film 119 and the thickness of the conductive film 118 (Ti film) for obtaining an excellent capacitor characteristic will be described.
The conductive film 118 and the SRO film 119 are formed to have thicknesses within the above range so that the (111) intensity of the seed PZT film 120 formed on the SRO film 119 can be increased. In other words, the seed PZT film 120 having excellent characteristics can be obtained. Further, a PZT film (below-described bulk PZT film 121) is formed with the seed PZT film 120 having excellent characteristics as an underlayer so that the ferroelectric capacitor having excellent characteristics can be obtained.
As the amount of Ti included in SRO is increased, the resistance of the SRO film is increased. When the resistance of the SRO film is large, a sufficient voltage cannot be applied to the PZT film, and therefore, a problem that the amount of signal is lowered arises. Accordingly, the thickness of the conductive film 118 is preferably determined so that the SRO film 119 after the RTA can cope with both crystallinity and conductivity. In other words, there is an optimum value according to the film thickness of the SRO film 119 for the thickness of the conductive film 118. Specifically, as described above, when the SRO film 119 of 2.5 nm is formed, the film thickness of the conductive film 118 made of Ti is preferably 1.5 nm.
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(14) The RTA is performed in an oxygen atmosphere to crystallize the seed PZT film 120. The RTA is performed under the conditions of e.g., 600° C. to 700° C. (preferably, 650° C.) and 30 seconds. By the RTA, the PZT film having a perovskite structure can be obtained. It should be noted that when the temperature of the thermal treatment is low, the seed PZT film 120 forms a pyrochlore structure of a paraelectric substance. When the crystalline structure of PZT is changed from the pyrochlore structure to the perovskite structure of the ferroelectric substance, a large energy is necessary. Therefore, desirably, the RTA is performed at temperatures of 600° C. or more, as described above, and PZT having the perovskite structure is formed without stopping, not via the pyrochlore structure.
It should be noted that during the film forming of the seed PZT film 120 having excessive Pb, when the RTA is performed in an oxygen atmosphere, Pb is desorbed, and at the same time, PbO having a low melting point promoting crystallization is added to the seed PZT film 120. As a result, stoichiometry is maintained to obtain a PZT film having excellent crystallinity.
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It should be noted that in the forming of the bulk PZT film 121, Pb(DPM)2, Ti(iOPr)2(DPM)2, and Zr(DiBM)4 are used for the source material of the CVD. Here, DPM is dipivaloylmethanate (chemical formula (CH3)3CCOCHCOC(CH3)3), iOPr is isopropoxide (chemical formula (OCH(CH3)2), and DiBM is diisobutylmethanate (chemical formula (CH3)2CH(CO)CH(CO—)CH(CH3)2)).
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(18) By a known method, a processing mask material (not shown) is formed on the Al2O3 film 123. More specifically, a silicon oxide film and a photoresist which become processing mask materials are successively stacked on the Al2O3 film 123 by e.g., the CVD method. Thereafter, the photoresist is patterned using the optical lithography method and the RIE method. With the patterned photoresist as a mask, the silicon oxide film formed on the Al2O3 film 123 is etched. Thereafter, the photoresist is removed to obtain the processing mask material having a desired pattern.
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It should be noted that the mask oxide film 127 is formed by the plasma CVD method using TEOS and oxygen (O2) for a source material at the film forming temperature of 420° C. In place of the plasma CVD method, the CVD method may be used. In that case, using ozone (O3), not oxygen, as a source gas, film forming is performed under the conditions of the film forming temperature of 350° C. to 500° C. (particularly preferably, 460° C.).
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It should be noted that as the first and the second protective films are relatively close to the PZT film, they are desirably formed by the sputtering method not discharging a gas deteriorating the PZT film such as hydrogen. On the other hand, as the third and the fourth protective films are relatively far from the PZT film, they are desirably formed using the ALD method or the CVD method which can perform dense film forming and secure a high step coverage although it discharges hydrogen.
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Thereafter, although the detailed description is omitted, upper wiring layers are successively formed to complete an FeRAM.
Next, referring to
The solid line plots the amount of read signal of an FeRAM formed by the method according to an embodiment of the present invention, and the dashed line plots the amount of read signal of an FeRAM for a reference sample. Here, the dielectric film of a ferroelectric capacitor of the reference sample is made by forming the seed PZT film and the bulk PZT film by the above two-stage CVD method on the lower electrode (Ir film).
It should be noted that in both samples of this embodiment and the reference sample, the total film thickness of the PZT film (the film thickness of the seed PZT film+the film thickness of the bulk PZT film) is fixed to 100 nm.
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When the film thickness of the seed PZT film is in a certain range in this manner, the following reasons why the amount of signal larger than the reference sample can be obtained can be considered.
When the film thickness of the seed PZT film 120 is too small (when it is smaller than the lower limit of a certain range), the seed PZT film 120 cannot sufficiently cover the entire surface of the SRO film 119, and therefore, a portion having insufficient crystallinity occurs. As a result, the deterioration of the characteristic (the reduction of the amount of signal) can be considered to occur.
On the other hand, when the film thickness of the seed PZT film 120 is too large (when it is larger than the upper limit of a certain range), Pb desorption caused by the thermal treatment after forming the seed PZT film 120 has distribution with respect to the thickness direction of the seed PZT film 120. As a result, the deterioration of the characteristic (the reduction of the amount of signal) can be considered to occur.
In other words, when the film thickness of the seed PZT film 120 is in a certain range, Pb desorption occurs due to the thermal treatment after film forming, but PZT having very excellent crystallinity is formed in other portion in which Pb desorption does not occur. As described above, this is because the crystallinity of the SRO film 119 as the underlayer of the seed PZT film 120 has the same perovskite structure as the PZT and the crystallinity of the SRO film 119 is improved by diffusing Ti into the SRO film 119. The PZT (the seed PZT film 120) having very excellent crystallinity is used as a crystal nucleus so that the bulk PZT film 121 can be formed by maintaining the crystallinity.
As described above, according to this embodiment, the PZT film having excellent crystallinity can be manufactured with high composition controllability, and therefore, the ferroelectric capacitor having excellent characteristics can be stably obtained. In addition, the amount of read signal larger than the FeRAM according to the comparative example can be obtained by adjusting the film thickness of the seed PZT film. This allows size reduction and higher integration of the FeRAM.
It should be noted that the following various modifications can be made to the above embodiments of the present invention.
In the above embodiments, the COP type FeRAM has been described, but the present invention is not limited to this and is also applicable to semiconductor devices using other ferroelectric capacitor.
In addition, in the above embodiments, the stacking film stacking the conductive film 118 and the SRO film 119 is formed as the underlayer of the seed PZT film 120, but in place of the stacking film, the SRO film into which Ti is doped may also be used.
Further, in the above embodiments, the conductive film 118 made of Ti is formed to promote the crystallization of the SRO film 119, but the conductive film 118 may also be formed using an element other than Ti. Specifically, V, W, Zr, Cr, Mg, Hf, Mo, Mn, Ta, or Nb may also be used.
Furthermore, in the above embodiments, the seed PZT film 120 made of PZT is formed as the seed layer of the bulk PZT film 121, but, as the seed layer, a PLZT ((PbxLay) (ZrzTi1-z)O3) film may also be used. Further, calcium (Ca) or strontium (Sr) may also be doped into the PLZT film.
While certain embodiments have been described, these embodiments have been presented by way of example only, and are not intended to limit the scope of the inventions. Indeed, the novel methods and systems described herein may be embodied in a variety of other forms; furthermore, various omissions, substitutions and changes in the form of the methods and systems described herein may be made without departing from the spirit of the inventions. The accompanying claims and their equivalents are intended to cover such forms or modifications as would fall within the scope and spirit of the inventions.
Number | Date | Country | Kind |
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2009-283006 | Dec 2009 | JP | national |