CN112063991A - Titanium nitride film and preparation method thereof - Google Patents
Titanium nitride film and preparation method thereof Download PDFInfo
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Abstract
The invention provides a titanium nitride film and a preparation method thereof, comprising the following steps: step 1, pretreating a substrate, and then placing the pretreated substrate into a plasma reaction cavity for heating; step 2, pulse NH is carried out in the plasma reaction cavity3Plasma; step 3, pulsing an organic metal precursor source of Ti into the plasma reaction cavity; step 4, repeating the step 3 and the step 4 until the thickness of the titanium nitride film deposited on the substrate meets the process requirement, and then performing N2Naturally cooling to room temperature under the condition to obtain a titanium nitride film; the invention can deposit the TiN film with uniform shape on the substrate with large aspect ratio and complex three-dimensional nano structure, solves the bottleneck problem which can not be solved by the traditional physical vapor deposition and chemical vapor deposition, and can also solve the problem that the traditional physical vapor deposition and chemical vapor deposition can not solveThe thickness of the TiN film is accurately controlled in the sub-nanometer level by controlling the ALD cycle number, and the preparation process is simple and easy to implement.
Description
Technical Field
The invention belongs to the technical field of nitride film preparation in the field of semiconductor materials and integrated circuits, and particularly relates to a titanium nitride film and a method thereof.
Background
As is well known, wear and corrosion are two of the most important factors of material and energy loss, and it is estimated that the economic loss caused by machine wear and corrosion failure in the main strut industry department of China is not superior to the economic loss. The loss caused by abrasion and corrosion can be greatly reduced by surface technology. Therefore, improving the wear resistance and corrosion resistance of materials has become one of the important research subjects in the material surface coating technology.
The hard film coating can reduce the friction and the abrasion of a workpiece, effectively improve the surface hardness, the toughness, the wear resistance, the corrosion resistance and the high-temperature stability, and greatly prolong the service life of a coating product, so that the hard film coating is widely applied to the fields of machine manufacturing, automobile industry, textile industry, geological drilling, mold industry, aerospace and the like.
TiN has gradually become a hot spot of hard coating research at home and abroad as a first industrialized and widely applied hard film material. The coating has the advantages of unique color, high hardness, wear resistance, low friction coefficient, electric and thermal conductivity, anti-curling property and the like, is widely used as a high-quality cutting tool, a clock shell, a decorative coating and the like, and recently, the application of the coating is expanded to more fields of optics, microelectronics, medicine and the like. With the continuous expansion of the application field of TiN films, the performance requirements of more uniform, more wear-resistant, more corrosion-resistant and more reliable are also provided for the TiN films. To meet the needs of this trend, many researchers have conducted a lot of research on the preparation technology and performance of TiN thin films.
The TiN film has high melting point, high hardness, excellent conductive heat conductivity and wear resistance and corrosion resistance, and has important application value and wide application prospect in cutters, molds, decorative materials and integrated circuits. The material is the first hard film material for realizing industrial application, and related research becomes a hot spot of hard layer research at home and abroad. With the intensive research on the TiN film, the process for preparing the TiN film is continuously developed, and the performance requirements of more uniformity, more wear resistance, more corrosion resistance and higher reliability are also provided for the TiN film. In order to meet the requirement of the development trend, a great deal of research work is carried out on the preparation technology and the performance of the TiN film by a plurality of researchers, at present, domestic research mostly focuses on the exploration of the preparation process of the TiN film and the wear resistance, and the research on the corrosion resistance is less.
However, to date, there are mainly the following methods for preparing TiN thin films: (1) the arc ion plating method has simple process, but has high deposition rate, difficult control of the thickness and uniformity of the film, easy formation of large particles in the film to influence the performance of the film, and no realization of three-dimensional uniform conformal coverage. (2) The TiN film is obtained by directly sputtering a TiN ceramic target by a magnetron sputtering method or sputtering a metal Ti target by a reactive magnetron sputtering method, the method has better film forming quality and plane uniformity, however, the ultrathin TiN film with accurate thickness is difficult to prepare, and especially uniform conformal coverage cannot be realized on a substrate with a three-dimensional structure. (3) The TiN film with higher quality can be prepared by the CVD method, but the deposition process needs high temperature and the controllability of the film thickness is poor. In summary, the existing methods for preparing metal TiN thin films all have the problems that the film thickness is difficult to control accurately and the step coverage is poor, and both the problems are the core factors for restricting the three-dimensional structure. However, in the rapid development of the present microelectronic technology, microelectronic circuits with a line width of 22nm and below have adopted a three-dimensional structure such as Fin-FET or Tri-Get. This marks that the transition of microelectronic circuits from planar structures to three-dimensional structures is a great trend, and how to solve the technical bottleneck problem (three-dimensional conformal uniformity) faced by the traditional PVD and CVD techniques after the transition from planar structures to three-dimensional structures is a key problem.
Disclosure of Invention
The invention aims to provide a titanium nitride film and a preparation method thereof, which solve the problem that the three-dimensional electrode of the existing three-dimensional nanometer device is difficult to prepare.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a titanium nitride film, which comprises the following steps:
step 1, pretreating a substrate, and then placing the pretreated substrate into a plasma reaction cavity for heating;
step 2, pulse NH is carried out in the plasma reaction cavity3Plasma;
step 3, pulsing an organic metal precursor source of Ti into the plasma reaction cavity;
step 4, repeating the step 3 and the step 4 until the thickness of the titanium nitride film deposited on the substrate meets the process requirement, and then performing N2Naturally cooling to room temperature under the condition to obtain the titanium nitride film.
Preferably, in step 1, the substrate is pretreated by the following specific method: putting the substrate into FH solution with the volume ratio of 1-10% for soaking and cleaning; putting the substrate into a plasma reaction cavity, and heating to (150-450) DEG C under the nitrogen atmosphere.
Preferably, in step 2, NH is pulsed into the plasma reaction chamber3Plasma, the specific process conditions are as follows: the pressure of the plasma reaction cavity is (500-1500) Pa; NH (NH)3The plasma flow is 50-200sccm, and the pulse time is 2-120 s; NH (NH)3The carrier gas of the plasma is high-purity Ar gas, and the flow rate is (20-100) sccm.
Preferably, in step 2, NH3And after the plasma pulse is finished, cleaning the plasma reaction cavity by using high-purity nitrogen.
Preferably, in step 3, the organometallic precursor source for Ti is pulsed into the plasma reaction chamber, and the specific process parameters are as follows:
the carrier gas of the organometallic precursor source of Ti is high purity N2Gas, N2The flow rate of the gas is (100-200) sccm; the pulse time of the organometallic precursor source of Ti is 0.1s to 60 s.
Preferably, in step 3, after the pulse of the organometallic precursor source of Ti is finished, the plasma reaction chamber is cleaned by using high-purity nitrogen gas.
Preferably, the organometallic precursor source of Ti is tetrakis (dimethylamino) titanium; NH (NH)3The plasma is composed of high purity NH3And high-purity Ar gas according to the volume ratio of 3: 1.
The titanium nitride film is prepared by the preparation method based on the titanium nitride film.
Compared with the prior art, the invention has the beneficial effects that:
according to the preparation method of the titanium nitride film, the uniform TiN film is deposited on the surface of the substrate with the plane or three-dimensional structure through Atomic Layer Deposition (ALD) equipment, the thickness and the components of the deposited film are very uniform, the surface is smooth, and the deposited film is an ultrathin film with the accurately controllable thickness; the difficult problem of electrode preparation of devices with complex three-dimensional structures is solved, for example, devices such as all-solid-state capacitor super devices with complex three-dimensional nano structures;
meanwhile, the TiN film which is uniform and has three-dimensional shape is deposited on a large-size substrate (such as 4 inches, 6 inches and 8 inches) by the preparation method of the invention;
in conclusion, the method can deposit the TiN film with uniform shape on the substrate with large aspect ratio and complex three-dimensional nano structure, solves the bottleneck problem which cannot be solved by the traditional physical vapor deposition and chemical vapor deposition, can accurately control the thickness of the TiN film in the sub-nanometer level by controlling the ALD cycle number, and has simple and easy preparation process.
The TiN thin film prepared by the method of the invention is determined to have the following properties through the analysis and test of instruments such as an electron energy loss spectroscopy (EDAX), a field emission scanning electron microscope (F scanning electron microscope), a four-probe and the like:
1. the TiN film has smooth surface, rough surface and small super-roughness;
2. TiN has low resistivity and is equivalent to other methods such as magnetron sputtering, CVD and the like;
3. the TiN film has uniform surface appearance and the sub-nanometer thickness of the film is accurately controllable.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) morphology of a TiN film prepared at 200 ℃ in example 1 of the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) morphology of a TiN film prepared at 250 ℃ in example 2 of the present invention;
FIG. 3 is a SEM image of TiN film prepared at 300 ℃ in example 3 of the present invention;
FIG. 4 is an X-ray energy spectrum analysis spectrum of a TiNx film prepared at 200 ℃ in example 1 of the present invention;
FIG. 5 is an X-ray energy spectrum analysis spectrum of a TiNx film prepared at 250 ℃ in example 1 of the present invention;
FIG. 6 is an X-ray energy spectrum analysis chart of a TiNx film prepared at 300 ℃ in example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
The invention provides a preparation method of a titanium nitride film, which comprises the following steps:
s101), putting the Si substrate into FH solution for soaking pretreatment so as to remove an oxide layer on the surface of Si;
s102), feeding the pretreated clean Si into a plasma reaction cavity, and heating to a preset temperature for later use;
s103), setting growth parameters of the plasma enhanced atomic layer deposition film;
s104), pulse NH is carried out to the inside of the plasma reaction cavity3Plasma, then cleaning the reaction cavity by high-purity nitrogen, and cleaning unreacted NH3Removing the plasma and the reaction by-products;
s105), pulsing an organic metal precursor source of Ti into the reaction cavity of the atomic layer deposition system, then cleaning the reaction cavity by using high-purity nitrogen, and discharging the organic metal precursor source and reaction byproducts which are not reacted;
s106), repeating the steps S104 and S105 until a TiN film with a preset thickness is deposited on the surface of the substrate, wherein the TiN film is uniform and has three-dimensional shape;
s107), after depositing the TiN film, filling high-purity (99.999%) N into the reaction cavity2And naturally cooling the TiN sample to room temperature, and taking the sample out of the cavity to obtain the titanium nitride film.
Further, in S105), the organometallic precursor source of Ti is tetrakis (dimethylamino) titanium (C)8H24N4Ti)；NH3The plasma is formed by high-purity NH3(99.9999%) and high purity Ar gasThe components are mixed according to the volume ratio of 3: 1.
Further, in S101), the substrate is placed into FH solution with the volume ratio of 1% -10% to be soaked for 3-15 seconds, and an oxide layer on the surface of the substrate is cleaned; the substrate is Si substrate, Pt substrate or SiO2A substrate.
Further, in S102, the cleaned substrate after pretreatment is sent into a vacuum reaction cavity of the atomic layer deposition equipment, and is heated to 150-450 ℃ in a nitrogen atmosphere for later use.
S103), the deposition parameter is that the pressure of the cavity is 500-1500 Pa; NH (NH)3The plasma flow is 50-200 sccm; NH (NH)3The carrier gas of the plasma is high-purity Ar gas, and the flow rate is 20-100 sccm; the carrier gas of the Ti precursor is high-purity N2The gas flow rate is 100 and 200 sccm.
S104), high purity NH3The pulse time of the gas plasma is 2s-120 s; the flushing time is 5s-200 s.
S105), the pulse time of the Ti precursor source is 0.1S-60S; the flushing time is 5s-120 s.
Example 1
A method of preparing a titanium nitride thin film, comprising the steps of:
s101), putting the Si substrate into a FH (FH) solution with the concentration of 1% for soaking for 3 seconds to remove an oxide layer on the surface of the Si substrate;
s102), conveying the cleaned pretreated Si substrate into a plasma reaction cavity, and heating to 200 ℃ for later use;
s103), setting growth parameters of the atomic layer deposition film of the plasma reaction cavity: the pressure of the cavity is 500 Pa; NH (NH)3Flow rate of 50sccm, high purity NH3The pulse time of the gas plasma was 2 s; NH (NH)3The carrier gas of the plasma is high-purity Ar gas, and the flow rate of the high-purity Ar gas is 20 sccm; tetrakis (dimethylamino) titanium (C)8H24N4Ti) pulse time of 0.1s, tetrakis (dimethylamino) titanium (C)8H24N4Ti) carrier gas is high-purity N2Gas, N2The flow rate of the gas is 100 sccm;
s104), pulse NH is carried out to the inside of the plasma reaction cavity3Plasma, then cleaning the reaction cavity by using high-purity nitrogen for 5s, and removing unreacted NH3Removing the plasma and the reaction by-products;
s105), pulse tetra (dimethylamino) titanium (C) into the plasma reaction cavity8H24N4Ti), then cleaning the reaction cavity by using high-purity nitrogen, wherein the purging time is 5s, and discharging the unreacted organic metal precursor source and reaction byproducts;
s106), repeating the steps S104 and S105 until a large-area uniform conformal TiN thin with a preset thickness is deposited on the surface of the Si substrate;
s107), after depositing the TiN film, filling high-purity (99.999%) N into the plasma reaction cavity2And taking the TiN sample out of the cavity after naturally cooling the TiN sample to room temperature.
Example 2
A method of preparing a titanium nitride thin film, comprising the steps of:
s101), putting the Pt substrate into a FH (hydrogen fluoride) solution with the concentration of 5% to soak for 8S so as to remove an oxide layer on the surface of Si;
s102), conveying the cleaned Pt substrate after pretreatment into a plasma reaction cavity, and heating to 300 ℃;
s103), setting growth parameters of the plasma enhanced atomic layer deposition film: the pressure of the cavity is 1000 Pa; NH (NH)3Plasma flow 100sccm, high purity NH3The pulse time of the gas plasma was 50 s; NH (NH)3The carrier gas of the plasma is high-purity Ar gas with the flow rate of 60 sccm; tetrakis (dimethylamino) titanium (C)8H24N4Ti) pulse time of 10s, tetrakis (dimethylamino) titanium (C)8H24N4Ti) carrier gas is high-purity N2Gas, N2The flow rate of the gas is 150 sccm;
s104), pulse NH is carried out to the reaction cavity of the atomic layer deposition system3Plasma, then cleaning the reaction cavity by using high-purity nitrogen gas, wherein the purging time is 80s, and unreacted NH is removed3Removing the plasma and the reaction by-products;
s105), pulsing an organic metal precursor source of Ti into a reaction cavity of the atomic layer deposition system, then cleaning the reaction cavity by using high-purity nitrogen, wherein the purging time is 80S, and discharging the unreacted organic metal precursor source and reaction byproducts;
s106), repeating the steps S104 and S105 until a large-area uniform conformal TiN thin with a preset thickness is deposited on the surface of the Pt substrate;
s107), after depositing the TiN film, filling high-purity (99.999%) N into the reaction cavity2And taking the TiN sample out of the cavity after naturally cooling the TiN sample to room temperature.
Example 3
A method of preparing a titanium nitride thin film, comprising the steps of:
s101), mixing SiO2Soaking the substrate in 10% FH solution for 15s to eliminate the oxide layer on the surface of Si;
s102), the pretreated clean SiO2The substrate is sent into a plasma reaction cavity and heated to 450 ℃;
s103), setting growth parameters of the plasma enhanced atomic layer deposition film: the pressure of the cavity is 1500 Pa; NH (NH)3Flow rate of 200sccm, high purity NH3The pulse time of the gas plasma was 120 s; NH (NH)3The carrier gas of the plasma is high-purity Ar gas, and the flow rate of the high-purity Ar gas is 100 sccm; tetrakis (dimethylamino) titanium (C)8H24N4Ti) pulse time of 60s, tetrakis (dimethylamino) titanium (C)8H24N4Ti) carrier gas is high-purity N2Gas, N2The flow rate of the gas is 200 sccm;
s104), pulse NH is carried out to the reaction cavity of the atomic layer deposition system3Plasma, then cleaning the reaction cavity by using high-purity nitrogen for 200s, and removing unreacted NH3Removing the plasma and the reaction by-products;
s105), pulsing an organic metal precursor source of Ti into a reaction cavity of the atomic layer deposition system, then cleaning the reaction cavity by using high-purity nitrogen, wherein the purging time is 120S, and discharging the unreacted organic metal precursor source and reaction byproducts;
s106), repeating the two steps of S104 and S105 until the SiO is formed2Depositing a large-area uniform conformal TiN film with a preset thickness on the surface of the substrate;
s107), after depositing the TiN film, filling high-purity (99.999%) N into the reaction cavity2And taking the TiN sample out of the cavity after naturally cooling the TiN sample to room temperature.
Example 4
A method of preparing a titanium nitride thin film, comprising the steps of:
s101), mixing SiO2Soaking the substrate in 10% FH solution for 15s to eliminate the oxide layer on the surface of Si;
s102), the pretreated clean SiO2The substrate is sent into a plasma reaction cavity and heated to 200 ℃;
s103), setting growth parameters of the plasma enhanced atomic layer deposition film: the pressure of the cavity is 1500 Pa; NH (NH)3Flow rate of 200sccm, high purity NH3The pulse time of the gas plasma was 120 s; NH (NH)3The carrier gas of the plasma is high-purity Ar gas, and the flow rate of the high-purity Ar gas is 100 sccm; tetrakis (dimethylamino) titanium (C)8H24N4Ti) pulse time of 60s, tetrakis (dimethylamino) titanium (C)8H24N4Ti) carrier gas is high-purity N2Gas, N2The flow rate of the gas is 200 sccm;
s104), pulse NH is carried out to the reaction cavity of the atomic layer deposition system3Plasma, then cleaning the reaction cavity by using high-purity nitrogen for 200s, and removing unreacted NH3Removing the plasma and the reaction by-products;
s105), pulsing an organic metal precursor source of Ti into a reaction cavity of the atomic layer deposition system, then cleaning the reaction cavity by using high-purity nitrogen, wherein the purging time is 120S, and discharging the unreacted organic metal precursor source and reaction byproducts;
s106), repeating the two steps of S104 and S105 until the SiO is formed2Depositing a large-area uniform conformal TiN film with a preset thickness on the surface of the substrate;
s107), precipitatingAfter the TiN film is accumulated, high-purity (99.999 percent) N is filled into the reaction cavity2And taking the TiN sample out of the cavity after naturally cooling the TiN sample to room temperature.
Example 5
A method of preparing a titanium nitride thin film, comprising the steps of:
s101), putting the Pt substrate into a FH (hydrogen fluoride) solution with the concentration of 5% to soak for 8S so as to remove an oxide layer on the surface of Si;
s102), conveying the cleaned Pt substrate after pretreatment into a plasma reaction cavity, and heating to 250 ℃;
s103), setting growth parameters of the plasma enhanced atomic layer deposition film: the pressure of the cavity is 1000 Pa; NH (NH)3Plasma flow 100sccm, high purity NH3The pulse time of the gas plasma was 50 s; NH (NH)3The carrier gas of the plasma is high-purity Ar gas with the flow rate of 60 sccm; tetrakis (dimethylamino) titanium (C)8H24N4Ti) pulse time of 10s, tetrakis (dimethylamino) titanium (C)8H24N4Ti) carrier gas is high-purity N2Gas, N2The flow rate of the gas is 150 sccm;
s104), pulse NH is carried out to the reaction cavity of the atomic layer deposition system3Plasma, then cleaning the reaction cavity by using high-purity nitrogen gas, wherein the purging time is 80s, and unreacted NH is removed3Removing the plasma and the reaction by-products;
s105), pulsing an organic metal precursor source of Ti into a reaction cavity of the atomic layer deposition system, then cleaning the reaction cavity by using high-purity nitrogen, wherein the purging time is 80S, and discharging the unreacted organic metal precursor source and reaction byproducts;
s106), repeating the steps S104 and S105 until a large-area uniform conformal TiN thin with a preset thickness is deposited on the surface of the Pt substrate;
s107), after depositing the TiN film, filling high-purity (99.999%) N into the reaction cavity2And taking the TiN sample out of the cavity after naturally cooling the TiN sample to room temperature.
The experimental results of the appearance observation of the scanning electron microscope shown in the figure 1-3 show that the TiN film obtained on the substrate by the method has obvious change in surface appearance, and the crystal grain size of the deposited TiN film is more uniform, smoother and more compact at 300 ℃.
Referring to FIGS. 4-6, TiNxThe X-ray energy spectrum analysis atlas result of the film shows that pure-phase TiN film can be obtained in the range of deposition temperature of 200-450 ℃.
The method has the advantages that the TiN film with uniform shape can be deposited on the substrate with large aspect ratio and complex three-dimensional nano structure, the bottleneck problem which cannot be solved by the traditional physical vapor deposition and chemical vapor deposition is solved, the thickness of the TiN film can be accurately controlled in the sub-nanometer level by controlling the ALD cycle number, the preparation process is simple and easy to implement, and the method is compatible with the existing semiconductor preparation process.
Claims (8)
1. A method for preparing a titanium nitride film is characterized by comprising the following steps:
step 1, pretreating a substrate, and then placing the pretreated substrate into a plasma reaction cavity for heating;
step 2, pulse NH is carried out in the plasma reaction cavity3Plasma;
step 3, pulsing an organic metal precursor source of Ti into the plasma reaction cavity;
step 4, repeating the step 3 and the step 4 until the thickness of the titanium nitride film deposited on the substrate meets the process requirement, and then performing N2Naturally cooling to room temperature under the condition to obtain the titanium nitride film.
2. The method for preparing a titanium nitride thin film according to claim 1, wherein in the step 1, the substrate is pretreated by: putting the substrate into FH solution with the volume ratio of 1-10% for soaking and cleaning; putting the substrate into a plasma reaction cavity, and heating to (150-450) DEG C under the nitrogen atmosphere.
3. According to claim 1The preparation method of the titanium nitride film is characterized in that in the step 2, pulse NH is carried out in the plasma reaction cavity3Plasma, the specific process conditions are as follows: the pressure of the plasma reaction cavity is (500-1500) Pa; NH (NH)3The plasma flow is 50-200sccm, and the pulse time is 2-120 s; NH (NH)3The carrier gas of the plasma is high-purity Ar gas, and the flow rate is (20-100) sccm.
4. The method of claim 1, wherein in step 2, NH is added to the titanium nitride film3And after the plasma pulse is finished, cleaning the plasma reaction cavity by using high-purity nitrogen.
5. The method according to claim 1, wherein in step 3, the Ti organometallic precursor source is pulsed into the plasma reaction chamber, and the specific process parameters are as follows:
the carrier gas of the organometallic precursor source of Ti is high purity N2Gas, N2The flow rate of the gas is (100-200) sccm; the pulse time of the organometallic precursor source of Ti is 0.1s to 60 s.
6. The method according to claim 1, wherein in step 3, after the pulse of the organometallic precursor of Ti is finished, the plasma reaction chamber is purged with high purity nitrogen.
7. The method according to claim 1, wherein the organometallic precursor source of Ti is tetrakis (dimethylamino) titanium; NH (NH)3The plasma is composed of high purity NH3And high-purity Ar gas according to the volume ratio of 3: 1.
8. A titanium nitride thin film produced by the method for producing a titanium nitride thin film according to any one of claims 1 to 7.
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