1. Field of the Invention
The present invention relates to a capacitor insulating film of a semiconductor device such as a Dynamic Random Access Memory, hereinafter referred to as a DRAM, and a method of forming the same.
Priority is claimed on Japanese Patent Application No. 2008-221491, filed Aug. 29, 2008, the content of which is incorporated herein by reference.
2. Description of the Related Art
In recent years, the size of a capacitor of a memory cell has been decreasing due to the advancement of minute processing techniques and high integration techniques of a DRAM. It has been difficult to acquire a sufficient capacity of the capacitor. The use of a capacitor insulating film of high dielectric constant in the capacitor is being developed. For example, Japanese Unexamined Patent Application, First Publications, No. 2004-146559 addresses that an SrTiOx film, where x is a positive number and hereinafter referred to as an STO film, is a powerful candidate for the capacitor insulating film.
The STO film has high dielectric constant when the thickness of the STO film is about 100 nm. But the dielectric constant of the STO film dramatically decreases if the STO film is thinned. It is difficult to make the STO film thick and at the same time make the capacity of the capacitor large.
Japanese Unexamined Patent Application, First Publications, No. 2004-146559 discloses a method of forming the STO film of high dielectric constant in the range of 130 to 170. The method is that a 20-nm-thick amorphous STO film is formed on a bottom electrode of polycrystalline Ru, and the amorphous STO film is treated with heat at in the range of 500° C. to 650° C. in an inert gas atmosphere. The amorphous STO film is formed on the bottom electrode at a high temperature of 420° C. by a Chemical Vapor Deposition method, hereinafter referred to as a CVD method. The high temperature causes a leakage by a damage of the bottom electrode.
In recent years, the thickness of the capacitor insulating film needs to be thinner when used in the DRAM of high capacity. The thickness of the capacitor insulating film needs to be about 10 nm in a generation of 40-nm-class process technology. When the capacitor insulating film is so thin, the dielectric constant of the capacitor insulating film decreases significantly, so further improvement is needed.
A capacitor insulating film may include, but is not limited to, strontium, titanium, and oxygen. The capacitor insulating film has a ratio of a spectrum intensity of (200) crystal face of the capacitor insulating film to a spectrum intensity of (111) crystal face of the capacitor insulating film in the range of 1.0 to 2.3. Each of the spectrum intensities of (200) crystal face and (111) crystal face is measured by an X-ray diffraction method.
A capacitor may include, but is not limited to, two electrodes, a capacitor insulating film disposed between the two electrodes. The capacitor insulating film may include, but is not limited to, strontium, titanium, and oxygen. The capacitor insulating film has a ratio of a spectrum intensity of (200) crystal face of the capacitor insulating film to a spectrum intensity of (111) crystal face of the capacitor insulating film in the range of 1.0 to 2.3. Each of the spectrum intensities of (200) crystal face and (111) crystal face is measured by an X-ray diffraction method.
A semiconductor device may include, but is not limited to, a capacitor. The capacitor may include, but is not limited to, two electrodes, a capacitor insulating film disposed between the two electrodes. The capacitor insulating film may include, but is not limited to, strontium, titanium, and oxygen. The capacitor insulating film has a ratio of a spectrum intensity of (200) crystal face of the capacitor insulating film to a spectrum intensity of (111) crystal face of the capacitor insulating film in the range of 1.0 to 2.3. Each of the spectrum intensities of (200) crystal face and (111) crystal face is measured by an X-ray diffraction method.
A method of fabricating a capacitor insulating film, the method may include, but is not limited to, forming a titanium oxide film, forming an amorphous strontium titanate film on the titanium oxide film, and forming a crystallized film that contains strontium, titanium and oxygen by carrying out a heat treatment in an inert gas atmosphere. The crystallized film has a crystal structure that a ratio of a spectrum intensity of (200) crystal face of the capacitor insulating film to a spectrum intensity of (111) crystal face of the capacitor insulating film is in the range of 1.0 to 2.3. Each of the spectrum intensities of (200) crystal face and (111) crystal face is measured by an X-ray diffraction method.
The above features and advantages of the present invention will be more apparent from the following description of certain preferred embodiments taken in conjunction with the accompanying drawings, in which:
The present inventors pursuit the cause of decreasing dielectric constant of the STO film with the reduction in thickness of the STO film, and find that (111) crystal face of the STO film is easily oriented and that the orientation of the (111) crystal face causes the decrease of the dielectric constant of the STO film.
The present inventors find that the (111) crystal face of the STO film becomes easily oriented with the reduction in thickness of the STO film, and that the easiness of the orientation of the (111) crystal face of the STO film causes the decrease of the dielectric constant of the STO film.
Even if the thickness of the STO film is reduced to 10 nm thick, the decrease of the dielectric constant of the STO film is prevented by forming the STO film with suppressing the orientation of the (111) crystal face of the STO film.
A capacitor insulating film of the invention is formed so that a spectrum intensity ratio (200)/(111) of the STO film is in the range of 1.0 to 2.3, where the spectrum intensity ratio (200)/(111) of the STO film is a ratio of a spectrum intensity of (200) crystal face of the STO film to a spectrum intensity of (111) crystal face of the STO film and each of the spectrum intensities of the (200) crystal face and (111) crystal face is measured by an X-ray diffraction method.
The STO film of the invention is formed by forming an amorphous STO film on a titanium oxide (TiOx) film and treating the amorphous STO film with heat in an inert gas atmosphere to be a crystal STO film.
Capacitor with large capacity can be fabricated easily by the method of the invention. A semiconductor memory device of high performance that has an excellent refresh characteristic can be fabricated easily by forming a memory cell of a DRAM using the capacitor that uses the capacitor insulating film of the invention.
The invention will be now described herein with reference to illustrative embodiments. Those skilled in the art will recognize that many alternative embodiments can be accomplished using the teaching of the present invention and that the invention is not limited to the embodiments illustrated for explanatory purpose.
Elemental ratio of each element of the STO film is not limited to a chemical formula SrTiO3 that means a stoichiometric ratio of Sr:Ti:O equals to 1:1:3, but may be any non-stoichiometric ratio as long as the STO film includes three elements, a strontium (Sr), a titanium (Ti), and an oxygen (O).
A material of the electrodes 1 and 2 is not limited to the ruthenium, but may be other metal film of high melting point such as a platinum (Pt) film or a titanium nitride (TiN) film, or a laminated film made of a plurality of metal films of high melting point.
A method forming the capacitor insulating film and the capacitor will be described.
[Process S1]
As illustrated in
[Process S2]
The titanium oxide (TiOx, where x is a positive number) film 4 is formed on the bottom electrode 1 by an Atomic Layer Deposition method, hereinafter referred to as an ALD method. Titanium (Ti) is oxidized by a cycle of heating the semiconductor substrate at 300° C., supplying a titanium (Ti) material gas for a predetermined time that is about 10 seconds, and supplying an ozone (O3) that is a combusting gas for a predetermined time. This cycle is a cycle of the ALD method, and by repeating the cycle for several times, the titanium oxide (TiOx) film 4 is formed with thickness in the range of 0.1 to 2.0 nm. The titanium (Ti) material gas may be a known material gas such as a tetrakis isopropoxy titanium (Ti(OCH(CH3)2)4), a tetrakis (2-methoxy-1-methyl-1-propoxo) titanium (Ti(MMP)4), a TiO(tmhd)2 where tmhd is 2,2,6,6-tetramethylheptane-3,5-dione, and a Ti(depd)(tmhd)2 where depd is diethylpentanediol, but not limited to these material gases. The combusting gas may be a water vapor (H2O) or an oxygen (O2) excited with plasma other than the ozone (O3).
[Process S3]
As illustrated in
In a conventional sequence of the ALD method, to fabricate the STO film of high dielectric constant, the strontium oxide film of high dielectric constant is formed first, and then the titanium oxide film and the strontium oxide film are formed alternately. The thickness of the titanium oxide film per one cycle of the conventional sequence of the ALD method is less than 0.1 nm. Even if the sequence of the ALD method is performed in reverse, the thickness of the formed titanium oxide film is not so thick as the present invention.
[Process S4]
As illustrated in
[Process S5]
Heat treatment at about 450° C. in a combusting gas atmosphere is performed to transform the STO film 3 to a more dense film. A gas including the oxygen (O2) can be used as the combusting gas. The heat treatment is preferable to be performed in a short time by the RTA method. The temperature of the heat treatment is preferable to be in the range of 400° C. to 500° C.
By performing the heat treatment, the boundary between the titanium oxide (TiOx) film 4 formed in the process S2 and the STO film 3a becomes unclear, and the titanium oxide (TiOx) film 4 and the STO film 3a becomes an integrated STO film 3. The process S5 that is the oxidizing heat treatment can be omitted depending on the electric characteristic needed by the STO film to be formed finally.
[Process S6]
As illustrated in
In the present invention, the orientation of the crystal face of the finally formed crystal STO film can be controlled by forming the titanium oxide film before forming the amorphous STO film.
When the thickness of the titanium oxide (TiOx) film is less than 1 nm, the spectrum intensity ratio (200)/(111) of the STO film increases as the thickness of the titanium oxide (TiOx) film increases. When the thickness of the titanium oxide (TiOx) film is more than 1 nm, the spectrum intensity ratio (200)/(111) of the STO film is constant. By forming the titanium oxide (TiOx) film first, the orientation of (200) crystal face of the STO film increases and the orientation of (111) crystal face of the STO film is suppressed. As is obvious from
In general, the real thickness of the capacitor insulating film is about 10 nm when the capacitor is disposed on the semiconductor device such as the DRAM.
As is described above, the spectrum intensity ratio (200)/(111) of the STO film measured by the X-ray diffraction method can be made in the range of 1.0 to 2.3 by forming the titanium oxide (TiOx) film at first when forming the capacitor insulating film using the strontium titanate (STO). As a result, the decrease of the dielectric constant can be suppressed even if the thickness of the STO film is about 10 nm, and the capacitor of large capacity can be easily fabricated.
In a conventional art, when the bottom electrode contains the ruthenium (Ru) as a major ingredient and the STO film is formed directly on the bottom electrode, a damage may occur on the surface of the ruthenium (Ru) in performing the oxidizing reaction of the strontium (Sr) in the process S3 of
In the present invention, the titanium oxide (TiOx) film is formed before the STO film is formed in the process S2, and the damage to the surface of the film containing the ruthenium (Ru) as a major ingredient can be suppressed. Then the STO film can be formed under high temperature condition as about 300° C. and the dense STO film can be easily formed. The leakage of the capacitor insulating film can be decreased easily in comparison with the conventional method in which the titanium oxide (TiOx) film is not formed.
The capacitor that uses the capacitor insulating film of the present invention can be applicable not only to the case when the electrode has a two-dimensional structure described in the first embodiment but also to the case when the electrode has a three-dimensional structure.
The capacitor having three-dimensional structure will be described by referring
As is described above, the capacitor with large capacity in the same area can be formed when the electrode of the capacitor has the three-dimensional structure described in
The third embodiment that applies the capacitor insulating film of the present invention to the capacitor in the memory cell of the DRAM will be described. The third embodiment is an example of the semiconductor device using the capacitor insulating film of the present invention.
A plurality of active regions 103 are disposed on a semiconductor substrate in a regular cycle. The semiconductor substrate is not illustrated in the figure. The plurality of active regions 103 are districted by a plurality of device isolation regions 102. Each of the device isolation regions 102 is formed by embedding an insulating film such as a silicon dioxide film in the semiconductor substrate using a known method. A plurality of gate electrodes 106 are disposed across the plurality of active regions 103. Each of the plurality of gate electrodes 106 behaves as a word line of the DRAM. An n-type diffused layer region is formed in a part of the plurality of active regions 103 that is not covered with the plurality of gate electrodes 106 by ion-implanting an impurity such as phosphorus. The n-type diffused layer region works as a source and a drain region of a MOS transistor.
A part enclosed by a broken line C of
In the layout of
A plurality of wiring layers, though not illustrated in the figure, are formed in the direction illustrated as a B-B′ line so as to contact the contact plug 107 and to intersect the gate electrode 106 at right angle in the fabricating process of later. Each of the plurality of wiring layers works as a bit line of the DRAM. Each of the contact plugs 108 and 109 is connected to the capacitor that is not illustrated in the figure and is formed using the capacitor insulating film of the present invention.
The interlayer insulating films 113, 116 and 118 are disposed for insulation between wirings. The wiring layer 119 is made of aluminum or copper and formed on the top side of the memory cell.
When the MOS transistor 101 turns ON, whether the capacitor 117 is charged or not can be judged through the wiring layer 112 that is the bit line, and the MOS transistor 101 acts as the memory cell of the DRAM that can store information.
The capacitor in the memory cell of the DRAM needs to have a large capacitor and to have a small amount of leakage.
As illustrated in
By using the capacitor insulating film of the present invention, the memory cell that has a superior charge retention property or a refresh property can be easily fabricated, and high-performance DRAM can be easily fabricated.
The capacitor insulating film of the present invention can be applied to devices other than the memory cell of the DRAM. For example, the capacitor insulating film of the present invention can be applied to a general semiconductor device such as a logic device that does not include the memory cell as long as the semiconductor device uses the capacitor.
It is apparent that the present invention is not limited to the above embodiments, but may be modified and changed without departing from the scope and spirit of the invention.
Number | Date | Country | Kind |
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2008-221491 | Aug 2008 | JP | national |
This application is a Divisional of U.S. patent application Ser. No. 12/548,010, filed Aug. 26, 2009, which claims priority to Japanese Patent Application No. 2008-221491, filed Aug. 29, 2008, the contents of all of which are incorporated herein by reference.
Number | Date | Country | |
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Parent | 12548010 | Aug 2009 | US |
Child | 13660537 | US |