Method of fabricating a semiconductor device including a reaction barrier film, a diffusion barrier film and a ferroelectric film
A method of fabricating a semiconductor device, is provided including forming an insulating film having an opening portion on a substrate having a transistor, filling a conductive film in the opening portion, forming a reaction barrier film functioning to prevent a reaction on the insulating film, and forming a diffusion barrier film on the conductive film. Next a first electrode is formed on the diffusion barrier film, a ferroelectric film, including at least one element of the group consisting of lead, barium and bismuth is formed on the first electrode after the step of forming the reaction barrier film, and a second electrode is formed on the ferroelectric film.
1. Field of the Invention
The present invention relates to a semiconductor device of an element using a ferroelectric thin film, particularly to a polarization inversion type non-volatile memory or a dynamic random access memory which is preferable to a large scale integrated circuit (LSI), and its fabrication method.
2. Description of the Prior Art
There are ferroelectric substances which have extremely large relative dielectric constant, ranging from several hundreds to several thousands. Therefore, when a thin film made of these ferroelectric substances is used in a capacitor insulating film, a capacitor is provided which as a small area and a large capacitance preferable to a large scale integrated circuit (LSI). Further, a ferroelectric substance is provided with a capacitor dielectric and its direction can be inverted by an outside electric field and accordingly, a non-volatile memory is provided by using the characteristic.
A memory is disclosed using a conventional ferroelectric substance in, for example, JP-A-5-90606. As shown by
In the meantime,
Further, as another conventional memory cell structure, a structure has been disclosed in JP-A-7-169854 in which, as shown by
When lead zirconate titanate (PZT) is used in a capacitor insulating film in the above-described method disclosed in JP-A-3-256358, according to an investigation conducted by the inventors, at a portion where PZT and a silicon oxide film, which is an interlayer insulating film are brought into direct contact with each other, a reaction is caused therebetween. The reaction is caused even at the low temperature of about 500° C., and particularly when PZT is formed at temperatures equal to or higher than 700° C., the silicon oxide layer completely reacts with PZT and a melted state is brought about. It becomes apparent that this phenomenon is caused by lead, which is a major constituent element of PZT.
Further, in respect of the above-described method disclosed in JP-A-7-14993, according to an investigation conducted by the inventors, it has been found that although Si3N4 in the adhesion layer reacts with PZT, similar to the silicon oxide film, when TiO2, ZrO2, Ta2O5 is used for the adhesion layer, the adhesion layer serves as a reaction barrier layer between PZT and the silicon oxide film, and therefore, the above-described problem of the reaction between PZT and the silicon oxide film can be resolved. However, according to the structure, it has been clearly found that since side faces of a diffusion barrier layer 249 disposed below a lower electrode are exposed, when the PZT film is formed by the CVD process or the like, necessitating a heated oxidizing atmosphere in the film forming operation, there poses a problem in which the diffusion barrier layer 249 is oxidized and the film is exfoliated. It has been found that, even in the case of using a sol-gel process, a sputtering process, a vapor deposition process or the like, a similar problem is posed in which, during the process of carrying out the heat treatment of crystallization, the diffusion barrier layer 249 is oxidized. It seems that although a metal nitride of TiN,(Ti, Al)N, WN, or the like is widely used in the diffusion barrier layer 249 and when the metal nitride is oxidized, nitrogen is discharged and therefore, the exfoliation of the film formed thereon becomes significant.
In the meantime, according to the method disclosed in JP-A-7-169854, when Ti is oxidized, the volume is expanded and exfoliation of the ferroelectric film is brought about.
It is an object of the present invention to achieve a semiconductor device which prevents a reaction between a ferroelectric film and an insulating film, and which also prevents film exfoliation and its fabrication method.
The above-described object is achieved by constituting a semiconductor device in which a reaction barrier film is provided between a ferroelectric film and an interlayer insulating film. Side faces of the diffusion barrier film and the ferroelectric film are not brought into contact with each other, and the side walls of a lower electrode and the ferroelectric film are brought into contact with each other.
By constructing the above-described constitution, in the case in which, for example, TiO2 is used for the reaction barrier film, when the film thickness is equal to or larger than 2 nm, it is effective in preventing a reaction between a silicon-species interlayer insulating film and lead included in a capacitor insulating film, even in a rapid heat treatment at about 700° C. which is needed in crystallizing a PZT film. Further, only the diffusion barrier film is embedded into the reaction barrier film, and, therefore, the side walls of the lower electrode can be utilized as a capacitor, which is particularly effective in the case of applying to the DRAM.
Further, the above-described object is achieved by embedding the diffusion barrier film in the interlayer insulating film as plugs and by interposing the reaction barrier film between the capacitor insulating film and the interlayer insulating film. Also in this structure, a lower electrode is formed on the plug, and accordingly, a ferroelectric film is installed from a side face to an upper face of the lower electrode. The side walls of the lower electrode can also be utilized as a capacitor, which is particularly effective in the case of using the invention in a DRAM.
Further, the above-described object is achieved by forming the reaction barrier film in a manner such that it functions to prevent a reaction on the interlayer insulating film, and, thereafter, forming the diffusion barrier film and the ferroelectric film. Before forming the diffusion barrier film and the ferroelectric film, the reaction barrier film is formed previously as an oxide, and, therefore, even when the reaction barrier film per se is formed by oxidizing a metal film, there poses no problem of exfoliation by volume expansion or the like.
Although the case in which PZT is used for the capacitor insulating film has been described, a similar effect is observed even in the case of using lead-species ferroelectric substance other than PZT or a Bi-species lamellar ferroelectric substance such as Bi4Ti3O12, Sr2Bi2Ta5O9 or the like. When using a Bi-species lamellar ferroelectric substance, generally, mutual diffusion with an interlayer insulating film becomes significant because the crystallizing temperature is higher than that of the Pb-species ferroelectric substance, and, accordingly, the use of a reaction barrier film becomes a necessity.
Further, it has been considered conventionally that in the case of a dielectric substance which does not include lead or bismuth, for example, strontium barium titanate (BST), the reaction with the silicon oxide film constituting the matrix of the lower electrode is not significant, and poses no serious problem. However, according to an investigation conducted by the inventors, it has been found that although the diffusion coefficient is smaller than that of Pb or Bi, Ba or Sr also diffuses into the SiO2, matrix. Therefore, it is found that the significance of installing the reaction barrier film is great, even in the case of using a film of BST-species.
The foregoing and other object, advantages, manner of operation, and novel features of the present invention will be understood from the following detailed description when read in connection with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
An explanation will be given of a preferred embodiment of the present invention with reference to
According to the structure, the ferroelectric thin film 71 and the upper electrode 72 are not separated into patterns in correspondence with respective memory cells, but are continuously present over a plurality of memory cells. With respect of the two layers, only the minimum fabrication necessary for operating a storage device (for example, a portion for separating a memory cell region from another region) is carried out, and the requirement for fabrication accuracy is considerably alleviated.
Further, the diffusion barrier layer 51 is embedded in the reaction barrier layer 43 and is not oxidized in the crystallization heat treatment of the ferroelectric thin film 71.
Next, a portion 25, where a bit line is brought into contact with the n-type diffusion layer at the surface of the substrate, is opened by using a known photolithography process and dry etching process (
Next, as shown in
Next, a Pt film 61 having a thickness of 100 nm is coated as a matrix electrode 61 by a sputtering process (
After removing the tungsten mask, a ferroelectric thin film 71 is formed (
An explanation will be given of a method of fabricating a memory cell by using the present invention, with reference to
As shown in
Next, a BST film 111 is piled up by 30 nm by using an MOCVD process, as shown in
Next, an explanation will be given with reference to
First, as shown in
Next, as shown by
By using a known photolithography process and dry etching process, contact holes are perforated from the portion 25 where the bit line is brought into contact with the n-type diffusion layer at the surface of the substrate and from the portion 26 where the store electrode is brought into contact with the n-type diffusion layer at the surface of the substrate leading to a peripheral circuit (
Next, an insulating film 191 of a silicon oxide film-species such as BPSG is piled up and flattened. According to the embodiment, the film thickness of the insulating film 191 is determined to be 250, nm and the insulating film 191 is flattened by a CMP process. By using a known photolithography process and dry etching process, a memory portion contact hole is perforated for connecting a store capacitance portion and a diffusion layer. At the same time, there are perforated contact holes for connecting the first wiring layer and a second wiring layer. A TiN layer having a thickness of 100 nm is piled up by a CVD process, and a TiN layer 192 is embedded into the contact holes by a CMP process.
Next, as shown in
Next, as shown in
An explanation will be given of a reading operation when a memory according to the present invention is used as a DRAM in reference to the circuit diagram shown in
Next, an explanation will be given of a reading and writing procedure based on JP-A-7-21784, when the memory of the present invention is used as ferroelectric involatile memory.
First, it is to be noted that the reading operation is the same as in the above-described case of DRAM.
In rewriting information in the ferroelectric involatile memory, polarization inversion of a ferroelectric film is carried out along with potential inversion of the store node SNI. The rewriting operation is the same as the reading operation until the signal line PCL1 is lowered from Vch to 0 and the sense amplifier is operated. Next, in order to write rewrite information prepared at the 10 line to the memory cell, the signal line CSLL is elevated from 0 to Vch. As a result, potentials of the bit line pair BL1 and BL1B are inverted. Since the word line WL1 is brought into an activated state, in accordance with the potential inversion of the bit line, the store node potential of the desired memory cell and the polarization direction of the ferroelectric film are inverted. In this way, after rewriting information, the rewiring operation is finished by a procedure similar to that of the reading operation. According to the reading and writing procedure, volatile information and involatile information are always rewritten coincidently, and, therefore, even when the power source is turned OFF, the information does not vanish.
Next, an explanation will be given of the operation of converting involatile information to volatile information when the power source is turned ON in the ferroelectric involatile memory. Before inputting the power source, all potential is at OV. In accordance with the power source ON, the plate PL1 is initialized to Vcc/2, and the signal lines CSP and CSN of the sense amplifier are initialized to 0 and Vcc. Further, the potential of the signal line PCL rises from 0 to Vcc, and, as a result, the potential of the bit line pair BL1 and BL1B is precharged to Vcc/2. At this time, the potential of the word line maintains OV and the store node SN1 is brought into a floating state such that the polarization direction of the ferroelectric film is not destroyed when the voltage of the plate is elevated. When the potentials of the plate P L1 and the bit line pair BL1 and BL1B are firmly stabilized to a potential of Vcc/2, the word lines WL are successively activated, and the store node SN1 is set to a potential of Vcc/2, the same as that of the plate PLI to thereby further stabilize the holding of polarization information. Successive to the above-described initializing an operation, the operation shifts to an operation of converting from involatile information to volatile information. First, the potential of PCL1 is set to OV, in a state in which all of the word lines are at OV, and the bit line is brought into a floating state. Next, the bit line is precharged to OV and is again brought into the floating state. Thereafter, when the word line WL1 is activated, current flows from the store node SN1 to the bit line, and the potential of the bit line is elevated. The amount of elevation is dependent on the polarization direction of the ferroelectric film. That is, even after elevating the potential of the bit line, the plate potential is higher, and, therefore, the polarization direction is aligned to one direction. The effective capacitance of the ferroelectric capacitor is larger in the case accompanied by inversion of polarization by activating the word line than in the case that is not accompanied by the inversion. As a result, the amount of potential elevation of the bit line is also larger. A dummy cell is installed for producing an intermediary value of the amount of potential elevation of the bit line in correspondence with the two polarization states in the compensating bit line BL1B, and the potential difference of the bit line pair BL1 and BL1B is detected and amplified by the sense amplifier SAI. By operating the sense amplifier, the bit line potential is charged to Vcc or O,and, as a result, the storage node SN1 is written with volatile information. Finally, the word line is deactivated, and, thereafter, the bit line potential is returned to Vcc/2 to thereby finish the series of operations. When the above-described operation is successively carried out for the respective word lines, the operation of converting from involatile information to volatile information is finished. According to the procedure, inversion of polarization of the ferroelectric film accompanied by an information reading operation can be executed only when the power source is inputted, and, accordingly, the deterioration of the ferroelectric film can be reduced. Further, there is no reduction in the reading speed caused by the time period required for the polarization inversion during normal use. Further, information at the time point when the power source is turned OFF is stored and the information can be revived when the power source is successively turned ON.
Although according to the above described embodiments, an explanation has been given by using a dielectric substance including lead as the ferroelectric material, in the case of a material reacting with silicon oxide at the temperature at which the ferroelectric film is formed, the present invention is effectively naturally applicable. Especially in the case of a material including bismuth, the present invention is particularly useful since a violent reaction is caused, as in the case of lead. That is, the preferred dielectric material for use in the present invention is an oxide dielectric including an element selected from lead and bismuth. As materials corresponding thereto other than PZT shown in the above-described examples, there are lead titanate (PbTiO3) lead barium zirconate titanate ((Ba, Pb) (Zr, Ti)03), barium lead niobate ((Ba, Pb)Nb2O6, strontium bismuth tantalite (SrBi2Ta2O9), bismuth titanate (Bi4Ti3O12), and barium strontium titanate zirconate (Ba, Sr)(Zr, Ti)O3. The present invention is applicable to all dielectric substances having these as a basic structure. That is, it may be an oxide described in the form of (A1A2 . . . ) (B1B2 . . . ) OX (A1=Pb, Bi; A2=Ca, Sr, Cd, Ba, La, Tl, Na, K; B1, B2 . . . =Ta, Ti, Zr, Hf, Fe, Nb, Sn, U, At, Mn, W, Yb, Sc, U. In, Sb, Co, Zn, Li, Mo, Ni, Co). Further, the present invention includes a case in which other elements are mixed with a material having major components of these.
Although as the reaction barrier layer, the titanium dioxide film is used in the above-described embodiments, a film having a major component of an oxide of elements selected from the above-described elements as B1 and B2, that is, Ta, Ti, Zr, Hf, Fe, Nb, Sn, U, At, Mn, W, Yb, Sc, U. In, Sb, Co, Zn, Li, Mo Ni and Co is also effective. Particularly, titanium oxide, aluminum, or bismuth silicate are effective.
Although according to the above-described embodiments, platinum is used as a material of an electrode, the electrode material can be implemented even with metals having major components of metals selected from Ru, Ir, Pd, Ni, Pt, and alloys of these, or oxides of elements selected from V, Cr, Fe, Ru, In, Sn, Re, Ir, Pt, Cu, and Pd.
Further, a diffusion barrier conductive layer may use a material selected from Ti, Ta, TiN, AlxTi1-x,N, and WN, or a plurality thereof by laminating them.
Although according to the embodiments, as a process of forming the reaction barrier layer, a sputtering process and thermal oxidation of a metal thin film are shown, other than a reactive sputtering in an oxygen including atmosphere, a thin film formed by a CVD process, or a sol/gel coating process, is also applicable.
According to the present invention, even when a dielectric substance i ncluding i ead is u sed as a capacitor insulating film, a reaction with an interlayer insulating film or a diffusion barrier layer can be restrained, and therefore, a highly integrated semiconductor storage device can be realized.
Claims
1. A method of fabricating a semiconductor device, said method comprising:
- a step of forming an insulating film having an opening portion on a substrate having a transistor;
- a step of filling a conductive film in the opening portion;
- a step of forming a reaction barrier film functioning to prevent a reaction on the insulating film;
- a step of forming a diffusion barrier film on the conductive film;
- a step of forming a first electrode on the diffusion barrier film;
- a step of forming a ferroelectric film including at least one element of the group consisting of lead, barium and bismuth on the first electrode after the step of forming the reaction barrier film; and
- a step of forming a second electrode on the ferroelectric film.
2. The method of fabricating a semiconductor device according to claim 1, wherein the diffusion barrier film is formed by forming the reaction barrier film on the insulating film and the conductive film, removing the reaction barrier film on the conductive film and embedding the diffusion barrier film in a region removed of the reaction barrier film.
3. A method of fabricating a semiconductor device, said method comprising:
- a step of forming an insulating film having an opening portion on a substrate having a transistor;
- a step of filling a conductive film in the opening portion;
- a step of forming a reaction barrier film functioning to prevent a reaction on the insulating film;
- a step of forming a diffusion barrier film on the conductive film after the step of forming the reaction barrier film;
- a step of forming a first electrode on the diffusion barrier film;
- a step of forming a ferroelectric film including at least one element of the group consisting of lead, barium and bismuth on the first electrode; and
- a step of forming a second electrode on the ferroelectric film.
4. The method of fabricating a semiconductor device according to claim 3,
- wherein the diffusion barrier film is formed by forming the reaction barrier film on the insulating film and the conductive film, removing the reaction barrier film on the conductive film and embedding the diffusion barrier film in a region removed of the reaction barrier film.
5. A method of fabricating a semiconductor device, said method comprising:
- a step of forming an insulating film having an opening portion on a substrate having a transistor;
- a step of filling a conductive film in the opening portion;
- a step of forming a reaction barrier film comprising an oxide on the insulating film;
- a step of forming a diffusion barrier film on the conductive film;
- a step of forming a first electrode on the diffusion barrier film;
- a step of forming a ferroelectric film including at least one element of the group consisting of lead, barium and bismuth on the first electrode; and
- a step of forming a second electrode on the ferroelectric film.
6. The method of fabricating a semiconductor device according to claim 5,
- wherein the diffusion barrier film is formed by forming the reaction barrier film on the insulating film and the conductive film, removing the reaction barrier film on the conductive film and embedding the diffusion barrier film in a region removed of the reaction barrier film.
7. The method of fabricating a semiconductor device according to claim 5,
- wherein the step of forming the reaction barrier film comprises a step of forming a metal film and a step of oxidizing the metal.
8. The method of fabricating a semiconductor device according to claim 5,
- wherein the step of forming the reaction barrier film is a step of forming the reaction barrier film by any of a reactive sputtering method in an oxygen including atmosphere, a CVD process and a sol/gel containing process.
Type: Application
Filed: Oct 20, 2004
Publication Date: Apr 7, 2005
Inventors: Kazuyoshi Torii (Hachioji-shi), Hiroshi Miki (Shinjuku-ku), Yoshihisa Fujisaki (Hachioji-shi)
Application Number: 10/968,077