CN114150293A - Deposition method and device for TiN and silicon dioxide double-layer coating - Google Patents

Deposition method and device for TiN and silicon dioxide double-layer coating Download PDF

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CN114150293A
CN114150293A CN202111414586.2A CN202111414586A CN114150293A CN 114150293 A CN114150293 A CN 114150293A CN 202111414586 A CN202111414586 A CN 202111414586A CN 114150293 A CN114150293 A CN 114150293A
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deposition
coating
tin
gas supply
sio
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朱权
李象远
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Sichuan University
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Sichuan University
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/401—Oxides containing silicon
    • C23C16/402—Silicon dioxide
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber

Abstract

A deposition method of TiN and silicon dioxide double-layer coating comprises the following steps: s1: carrying out pretreatment operation on the sample; s2: depositing a TiN coating on the sample piece after the pretreatment operation by using TiN raw material gas in a CVD mode; s3: depositing SiO by MOCVD deposition mode through ethyl orthosilicate self-decomposition reaction on the sample piece on which the TiN coating is deposited2Coating; s4: and cooling the sample piece. A deposition device of TiN and silicon dioxide double-layer coating comprises a CVD gas supply system, an MOCVD gas supply system and a deposition system; the CVD gas supply system and the MOCVD gas supply system are both connected to the deposition system; the deposition of TiN coating and SiO are carried out in the deposition system2Deposition of a coating, the CVD gas supply system providing TiN feed gas to the deposition system during deposition of a TiN coating in the deposition systemThe MOCVD gas supply system carries out SiO in the deposition system2Providing SiO to the deposition system during deposition of the coating2A raw material gas. The formed coating has good fracture toughness and compactness, and effectively inhibits coking.

Description

Deposition method and device for TiN and silicon dioxide double-layer coating
Technical Field
The invention relates to the field of material surface treatment and coating, in particular to a deposition method and a deposition device for a TiN and silicon dioxide double-layer coating.
Background
In the cooling protection of the engine, the active cooling of the fuel oil can realize energy regeneration because of high cooling efficiency, and does not need to carry extra coolant, thereby becoming a cooling scheme with extremely high potential. This technique has been widely validated, however, the problem of coking associated with fuel cracking has been a significant impediment to the application of this technique. Among them, filamentous coke catalytically produced by Fe and Ni elements in the matrix becomes a main cause of cooling channel blockage because of its high growth rate and the ability to trap coke in the bulk phase. In addition, in the field of ethylene production by hydrocarbon cracking, the presence of coke reduces the internal diameter of the furnace tubes and lowers the heat transfer coefficient, thereby increasing the fluid pressure drop and energy consumption, with the attendant carburization process leading to a reduction in furnace life.
The preparation of chemically inert coatings on substrates is an effective method to inhibit metal-catalyzed coking and carburization effects and has been extensively studied. Long-term operation of the fuel cracking system will inevitably lead to carbon deposition and the necessary decoking process will introduce oxygen molecules threatening the integrity of the coating. In addition, most metal oxide coatings having oxidation resistance have poor fracture toughness and large differences in the coefficient of thermal expansion of the substrate, and are prone to cracking and peeling. Thus, while the coke inhibition and service life of the coating are significantly improved, the performance after the coke-decoking cycle is not clear and there is a pressing need to evaluate the durability of the coating under the coke-decoking cycle.
In the active cooling application, the coating becomes a main means for inhibiting coking, and the typical TiN coating has good fracture toughness and compactness, effectively isolates metal catalytic elements in a matrix and can effectively inhibit coking. However, the single-layer TiN coating has poor oxidation resistance, and the gaps among crystal grains provide channels for the diffusion of O atoms and C atoms, so that the coating is damaged in the circulating use, and the oxidation phenomenon can occur at 650 ℃. The metal oxide coating with oxidation resistance has poor fracture toughness and low thermal expansion coefficient (alpha (Er)2O3)＝7.2×10-6K-1,α(Al2O3)＝6.5×10-6K-1,α(SiO2)＝0.5×10-6K-1) The difference between the thermal expansion coefficient of the substrate and the thermal expansion coefficient of the substrate is large (alpha is 16 multiplied by 10)-6K-1) High mismatch, and easy cracking and falling off.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a deposition method and a deposition device for a TiN and silicon dioxide double-layer coating, wherein the formed coating has good fracture toughness and compactness, is not easy to crack and fall off, effectively inhibits coking and has strong oxidation resistance.
The purpose of the invention is realized by the following technical scheme:
a deposition method of TiN and silicon dioxide double-layer coating comprises the following steps:
s1: carrying out pretreatment operation on the sample;
s2: depositing a TiN coating on the sample piece after the pretreatment operation by using TiN raw material gas in a CVD mode;
s3: depositing SiO by MOCVD deposition mode through ethyl orthosilicate self-decomposition reaction on the sample piece on which the TiN coating is deposited2Coating;
s4: and cooling the sample piece.
Further, the pretreatment operation comprises stain removal cleaning, acid washing, rinsing, acetone cleaning and drying.
Further, the TiN raw gas comprises N2Raw material gas, H2Raw gas and TiCl4Steam;
further, in the step S2, after the sample piece after the pretreatment operation is heated to the temperature required for TiN coating deposition, TiN raw material gas is introduced into the sample piece after the pretreatment operation to perform TiN coating deposition.
Further, in the step S3, the dilution gas is introduced into the sample and the temperature of the sample is reduced to SiO2After the temperature required by the coating deposition is reached, TEOS vapor is introduced into the sample piece to carry out SiO2And (4) depositing a coating.
A deposition apparatus for TiN and silicon dioxide double layer coating comprises CVD gas supplyA reaction system, an MOCVD gas supply system and a deposition system; the CVD gas supply system and the MOCVD gas supply system are both connected to the deposition system; the deposition of TiN coating and SiO are carried out in the deposition system2Deposition of the coating, the CVD gas supply system providing TiN feed gas for the deposition system during deposition of the TiN coating in the deposition system, and the MOCVD gas supply system performing SiO deposition in the deposition system2Providing SiO to the deposition system during deposition of the coating2A raw material gas.
Further, the CVD gas supply system includes N2Feed gas supply line, H2A raw gas supply pipe, a first carrier gas supply pipe, TiCl4An evaporator and a gas mixing container, wherein the output end of the first carrier gas supply pipeline is connected with TiCl4Evaporator, said N2Feed gas supply line, H2Feed gas supply line and TiCl4The output end of the evaporator is connected with a gas mixing container, and the gas mixing container is connected with a deposition system.
Further, the TiCl4And a first heating belt is arranged on a pipeline connecting the output end of the evaporator and the gas mixing container and a pipeline connecting the gas mixing container and the deposition system.
Further, the MOCVD gas supply system comprises a diluent gas supply pipeline, a second carrier gas supply pipeline and a TEOS evaporator; the output end of the second carrier gas supply pipeline is connected with the TEOS evaporator, and the output ends of the dilution gas supply pipeline and the TEOS evaporator are both connected to the deposition system.
Furthermore, a second heating belt is arranged on a pipeline connecting the output end of the TEOS evaporator and the deposition system.
The invention has the beneficial effects that:
the coating formed by the invention has good fracture toughness and compactness, is not easy to crack and fall off, effectively inhibits coking, and has strong oxidation resistance.
Drawings
FIG. 1 is a schematic structural diagram of an apparatus for depositing a dual-layer coating of TiN and silicon dioxide;
FIG. 2 is a graph of HT-XRD spectra before and after testing of a sample having only TiN coating;
FIG. 3 is a photograph of a sample piece having only TiN coating before and after XRD testing;
FIG. 4 shows a structure having TiN and SiO2HT-XRD spectrograms of a sample piece with the double-layer coating before and after testing;
FIG. 5 shows a structure having TiN and SiO2Photos of a sample piece with the double-layer coating before and after XRD test;
FIG. 6 is an initial 3D profile and roughness map of a prototype part with only TiN coating in white light interference and roughness results;
FIG. 7 is a 3D profile and roughness plot of a sample with only TiN coating after a single cycle of white light interference and roughness results;
FIG. 8 is a graph of 3D profile and roughness after double cycling of a sample with only TiN coating in white light interference and roughness results;
FIG. 9 is a graph of 3D profile and roughness after three cycles for a sample with only TiN coating in white light interference and roughness results;
FIG. 10 shows the results of white light interference and roughness with TiN and SiO2An initial 3D profile and roughness map of a double-coated sample;
FIG. 11 shows the results of white light interference and roughness with TiN and SiO23D contour and roughness map after single cycle of the sample piece of the double-layer coating;
FIG. 12 shows the results of white light interference and roughness with TiN and SiO2A 3D contour and roughness map of a double-coated sample after double circulation;
FIG. 13 shows the results of white light interference and roughness with TiN and SiO23D contour and roughness map of the double-layer coated sample after three cycles;
fig. 14 is an initial NST acoustic signal, friction signal and depth map of a sample with only TiN coating in nano-scratch results;
fig. 15 is a graph of NST acoustic signal, friction signal and depth after a single cycle of a sample with only TiN coating in nano-scratch results;
FIG. 16 shows the results of nano-scratches with TiN and SiO2Initial NST Acoustic Signal, Friction of double-coated sampleSignal and depth maps;
FIG. 17 shows the results of nano-scratches with TiN and SiO2NST acoustic signals, friction signals and depth maps of the sample with the double-layer coating after single circulation;
FIG. 18 is a bare sample, a sample with only TiN coating, with TiN and SiO2The coking amount and the coking inhibition effect of the sample piece with the double-layer coating are shown.
In the figure, 1-CVD gas supply system, 11-N2Raw gas supply pipeline, 12-H2A raw gas supply line, 13-a first carrier gas supply line, 14-TiCl4A vaporizer, a 15-gas mixing container, a 16-first heating zone, a 2-MOCVD gas supply system, a 21-dilution gas supply pipe, a 22-second carrier gas supply pipe, a 23-TEOS vaporizer, a 24-second heating zone, a 3-deposition system, a 31-reaction chamber, a 32-purification plant, a 41-drying pipe, a 42-needle valve, a 43-gas flow meter, and a 44-temperature controller.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It is to be noted that the features in the following embodiments and examples may be combined with each other without conflict.
It should be noted that the drawings provided in the following embodiments are only for illustrating the basic idea of the present invention, and the components related to the present invention are only shown in the drawings rather than drawn according to the number, shape and size of the components in actual implementation, and the type, quantity and proportion of the components in actual implementation may be changed freely, and the layout of the components may be more complicated.
The first embodiment is as follows:
as shown in fig. 1 to 18, a deposition method of a TiN and silicon dioxide dual-layer coating includes the following steps:
s1: carrying out pretreatment operation on the sample;
the pretreatment operation comprises stain removal and cleaning, acid washing, rinsing, acetone cleaning and drying.
Cleaning stains, and removing dust and fine impurities in the processing process; removing an oxide film and a corrosion product on the inner wall by acid washing; rinsing with deionized water with higher purity to remove surface residues; cleaning with acetone to remove oil stain and other organic substances; the drying operation is to put the sample piece into an oven to be dried at 80 ℃.
S2: depositing a TiN coating on the sample piece after the pretreatment operation by using TiN raw material gas in a CVD mode;
the TiN raw gas comprises N2Raw material gas, H2Raw gas and TiCl4Steam;
the deposition mechanism of the TiN coating is as follows:
2TiCl4+N2+4H2＝2TiN+8HCl
heating the sample after the pretreatment operationToAnd (3) after the temperature required by the deposition of the TiN coating is 800 ℃, introducing TiN raw material gas into the sample piece subjected to the pretreatment operation to deposit the TiN coating.
The TiCl4The steam is introduced along with the first carrier gas, and the introduced TiCl4The steam is heated during the introduction.
S3: performing Tetraethoxysilane (TEOS) self-decomposition reaction on the sample piece on which the TiN coating is deposited, and depositing SiO in an MOCVD (metal organic chemical vapor deposition) mode2Coating;
the SiO2The deposition mechanism of the coating is as follows:
TEOS→SiO2+C2H4+H2O
after the TiN coating deposition process is finished, introducing diluent gas into the sample piece and cooling the sample piece to SiO2After the temperature required for coating deposition, namely 700 ℃, TEOS steam is introduced into the sample piece for SiO2And (4) depositing a coating.
And introducing the TEOS steam along with a second carrier gas, and heating the introduced TEOS steam in the introducing process.
S4: and cooling the sample piece.
A TiN and silicon dioxide double-layer coating deposition device comprises a CVD gas supply system 1, an MOCVD gas supply system 2 and a deposition system 3; the CVD gas supply system 1 and the MOCVD gas supply system 2 are both connected to a deposition system 3; the deposition of TiN coating and SiO are carried out in the deposition system 32The CVD gas supply system 1 supplies TiN raw gas to the deposition system 3 when the deposition of TiN coating is carried out in the deposition system 3, and the MOCVD gas supply system 2 carries out SiO deposition in the deposition system 32Providing SiO to the deposition system 3 during deposition of the coating2A raw material gas.
The deposition system 3 comprises a reaction chamber 31, wherein the reaction chamber 31 is a box-type furnace with a constant temperature zone as long as 1.6m, and a tubular reactor is arranged in the box-type furnace.
The output end of the reaction chamber 31 is connected with a purification plant 32, and the purification plant 32 is provided with a tail gas treatment device for treating tail gas.
The CVD gas supply system 1 provides TiN raw gas for deposition of TiN coating;
the TiN raw gas comprises N2Raw material gas, H2Raw gas and TiCl4Steam;
the CVD gas supply system 1 includes N2Raw gas supply pipeline 11, H2A raw gas supply pipe 12, a first carrier gas supply pipe 13, TiCl4An evaporator 14 and a gas mixing container 15, wherein the output end of the first carrier gas supply pipeline 13 is connected with TiCl4Evaporator 14, said N2Raw gas supply pipeline 11, H2Feed gas supply line 12 and TiCl4The output end of the evaporator 14 is connected with a gas mixing container 15, and the gas mixing container 15 is connected with the deposition system 3.
The TiCl4The pipeline of the output end of the evaporator 14 connected with the gas mixing container 15 and the pipeline of the gas mixing container 15 connected with the deposition system 3 are provided with first heating belts 16.
The TiCl4 A temperature controller 44 is connected to the evaporator 14.
N2N is supplied from a raw material gas supply line 112Raw material gas, H2Feed gas supply line 12 supplies H2A source gas, and a first carrier gas supply line 13 supplies a first carrier gas;
said N is2Raw gas supply pipeline 11, H2The source gas supply line 12 and the first carrier gas supply line 13 are each provided with a drying pipe 41, a needle valve 42, and a gas flow meter 43.
The drying tube 41 is a molecular sieve drying tube 41.
The first carrier gas is H2And (4) a carrier gas.
N2The raw material gas is introduced into N at a flow rate of 1235mL/min as one of the reaction gases2A raw gas supply line 11; h2Introducing H into the raw material gas at the flow rate of 821mL/min2The raw gas supply pipeline 12 participates in the reaction at the same time; the first carrier gas is introduced into the first carrier gas supply pipe 13 at a flow rate of 896mL/min and passes through TiCl4The evaporator 14 carries TiCl out4The vapor participates in the deposition reaction. N is a radical of2Raw material gas, H2Raw material gas and H2The carrier gas passes through the molecular sieve drying tube 41, the needle valve and the mass flow meter in sequence.
Putting the sample piece subjected to the pretreatment operation into a tubular reactor, and heating at a heating rate of 10 ℃/min; starting the first heating belt 16 to heat to 80 ℃ after the temperature rises to 800 ℃, sequentially opening the feed gas until H is observed2And (4) timing after the carrier gas can smoothly flow until the deposition process of the TiN coating is finished.
The MOCVD gas supply system 2 is SiO after the TiN coating deposition process is finished2Deposition of the coating to provide SiO2Raw material gas;
the SiO2The feed gas comprises TEOS vapor;
the MOCVD gas supply system 2 comprises a diluent gas supply pipe 21, a second carrier gas supply pipe 22 and a TEOS evaporator 23; the output end of the second carrier gas supply pipe 22 is connected to a TEOS evaporator 23, and the output ends of the dilution gas supply pipe 21 and the TEOS evaporator 23 are both connected to the deposition system 3.
And a second heating belt 24 is arranged on a pipeline connecting the output end of the TEOS evaporator 23 with the deposition system 3.
The TEOS evaporator 23 is connected to a temperature controller 44.
The diluent gas supply line 21 supplies diluent gas, and the second carrier gas supply line 22 supplies second carrier gas.
The dilution gas supply line 21 and the second carrier gas supply line 22 are provided with a drying tube 41, a needle valve 42, and a gas flow meter 43.
The diluent gas is N2Diluent gas, second carrier gas is N2And (4) a carrier gas.
N2Introducing the diluent gas into the deposition system 3 at a flow rate of 1023mL/min, cooling and maintaining the oxygen-free atmosphere in the device until the deposition temperature reaches SiO2The temperature required for deposition.
Turn on N2Diluting gas and switching the cooling program to cool to SiO2The temperature required for coating deposition, namely 700 ℃, is introduced after the specified temperature is reached2SiO by carrier gas2Deposition of the coating, N being turned off after the deposition has ended2And naturally cooling the carrier gas, and taking out the sample after cooling to obtain the coating sample.
TiN and SiO double-layer coating prepared by deposition method and device of TiN and silicon dioxide double-layer coating2The durability of the coating was evaluated for each of the two-layer coated samples and the conventional samples having only a TiN coating.
The durability evaluation of the coating comprises the steps of carrying out a fuel oil cracking process and a decoking process on the sample piece in sequence.
The comparison shows that: as shown in fig. 2 to 5, it can be seen from the results of the high temperature in situ XRD test that the sample piece with only TiN coating is completely oxidized at an oxidation temperature of 750 ℃, and the sample piece with only TiN coating is significantly exfoliated and oxidized after the test. In contrast, with TiN and SiO2The sample piece with the double-layer coating has no diffraction peak of an oxidation product at the oxidation temperature of 900 ℃, and the appearance of the coating is still compact and does not fall off after the test, which indicates that the coating is not oxidized.
The durability evaluation of the coating also comprises the steps of carrying out coking and decoking on the sample piece in a circulating way.
According to the cycle of coking-coke cleaning,samples subjected to 1, 2, 3 cycles were subjected to white light interferometry for surface roughness determination. Structures as shown in FIGS. 6-13, samples with TiN coating alone experienced a significant roughness increase after cycling, as opposed to TiN and SiO2The sample piece with the double-layer coating always has excellent coating roughness. Illustrating the presence of TiN and SiO2The sample piece with the double-layer coating still remains intact after going through a coking and decoking cycle, which is beneficial to inhibiting the improvement of coking performance.
The binding force of the coating after the coking and decoking cycles is judged through a nano scratch test, as shown in figures 14-17, the result shows that compared with a sample piece only provided with a TiN coating, the coating has TiN and SiO2The critical load of the sample piece with the double-layer coating does not obviously decrease, which shows that the sample piece with the TiN and SiO has2The sample piece with the double-layer coating still has excellent binding force performance after being subjected to coking-decoking cycle use.
The amount of coking in the coated tube during the coking-decoking cycle was also determined as shown in FIG. 18, which shows in FIG. 18 a bare sample, a sample having only a TiN coating, a sample having TiN and SiO during the coking-decoking cycle2Coke quality and coke inhibition of the double coated samples. It can be found that the silicon nitride has TiN and SiO2The sample piece with the double-layer coating has extremely excellent coking inhibition performance, and the average coking inhibition rate can reach more than 92 percent and is far higher than the coking inhibition performance of the sample piece with only the TiN coating.
With TiN and SiO2The sample piece with the double-layer coating has good fracture toughness and compactness, is not easy to crack and fall off, effectively inhibits coking, and has strong oxidation resistance.
Coating oxide (SiO)2Coating) is coated on the inner TiN coating to play the advantages of the two coatings, on one hand, the inner TiN coating can effectively reduce the mismatching degree of the matrix and the oxide, and on the other hand, the outer oxide coating (SiO)2Coating) can effectively block the diffusion of oxygen element, and plays a role in oxidation resistance. Selection of SiO2As an outer oxide coating, the amorphous compact property of the coating can effectively isolate the diffusion of O element, and the oxidation resistance effect is achieved. In addition, the high crystallization temperature of the coating can ensure that the coating does not generate light during the application processAnd the crystallization process is generated, so that the stability of the coating is ensured.
For long-range channels, chemical vapor deposition is the main way to prepare the channel inner coating with TiCl4-H2-N2The preparation of TiN coatings by CVD as a raw material gas is a well established preparation process. For outer SiO layer2The method of (1) if CVD is used, oxygen-containing components are introduced to oxidize the inner TiN layer, so that MOCVD is used to prepare the outer SiO layer2The self-decomposition reaction system can ensure that the SiO is successfully prepared in the oxygen-free atmosphere2. Thus, efficient application of the bilayer coating is achieved by the innovative combined CVD + MOCVD deposition process.
And heating the coating by adopting the same sleeve furnace for deposition, debugging the program to meet the deposition temperature of the two deposition modes in sequence, and performing a deposition experiment after the specified deposition temperature is reached.
Due to the self-decomposition reaction characteristic of TEOS, a proper deposition temperature needs to be explored, so that the requirement of depositing SiO is met on one hand2On the other hand, it is necessary to avoid the problem that the organic precursor is decomposed in the gas phase due to the excessive temperature, so that a complete and compact coating cannot be formed. In order to solve the problem, a design scheme of hot wall deposition is adopted, redundant heating steps are not carried out before gas enters a constant temperature area, a sample piece needing to be coated is placed at the front end of a constant temperature section, and gas phase reaction in a deposition chamber is avoided.
According to the scheme of the embodiment, the coating which is strong in integrity and strong in durability can be successfully prepared, metal catalytic coking on the surface of the substrate can be effectively inhibited, the pipeline is prevented from being blocked, and the running time of a supercritical cracking experiment is prolonged.
The passivation coating is produced in a variety of ways, and chemical vapor deposition is certainly the most feasible way for internal channels with high aspect ratios. TiN produced by the chemical vapor deposition method has been shown to have good bonding force and fracture toughness, but its weak oxidation resistance results in easy oxidation in repeated use. Therefore, the TiN coating is used as the intermediate layer in the embodiment to reduce the thermal expansion coefficient mismatch between the outer layer oxide and the substrate, and meanwhile, the TiN coating is used as the auxiliary layer to provide the indefinite high-density characteristicFormal oxide (SiO)2Coating) as an outer insulating layer to obtain TiN and SiO2Double-layer coating to realize the effect of strong oxidation resistance.
To avoid preparing SiO layer2The inner TiN layer is oxidized, the invention adopts metal organic vapor deposition (MOCVD) to prepare TiN/SiO2Outer SiO layer of double-layer coating2The self-decomposition reaction mechanism of the organic precursor can prepare the required oxide coating under the anaerobic condition. Therefore, a combined chemical vapor deposition method is adopted to combine TiN coating and SiO2The advantages of the coating are that the TiN/SiO with oxidation resistance is successfully prepared2Double-layer composite coating.
The performance requirement of the passivation coating is increasingly improved, and the TiN/SiO is successfully prepared by a combined chemical vapor phase method aiming at the performance defect of the existing single-layer coating2Double-layer composite coating. The method is characterized in that: the SiO can be prepared on the basis of not oxidizing the inner TiN coating layer by using a CVD + MOCVD combined vapor deposition mode2(ii) a The inner TiN layer successfully reduces the thermal expansion coefficient mismatching between the outer oxide layer and the substrate, and the outer SiO layer2Effectively isolating the diffusion of O element and improving the oxidation resistance of the coating.
The above-mentioned embodiments only express the specific embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.

Claims (10)

1. A deposition method of TiN and silicon dioxide double-layer coating is characterized in that: the method comprises the following steps:
s1: carrying out pretreatment operation on the sample;
s2: depositing a TiN coating on the sample piece after the pretreatment operation by using TiN raw material gas in a CVD mode;
s3: depositing SiO by MOCVD deposition mode through ethyl orthosilicate self-decomposition reaction on the sample piece on which the TiN coating is deposited2Coating;
s4: and cooling the sample piece.
2. The method of claim 1, wherein: the pretreatment operation comprises stain removal and cleaning, acid washing, rinsing, acetone cleaning and drying.
3. The method of claim 1, wherein: the TiN raw gas comprises N2Raw material gas, H2Raw gas and TiCl4And (4) steam.
4. The method of claim 1, wherein: and step S2, heating the sample piece after the pretreatment operation to the temperature required by the deposition of the TiN coating, and introducing TiN raw gas into the sample piece after the pretreatment operation to deposit the TiN coating.
5. A method of depositing a TiN and silicon dioxide bilayer coating according to any one of claims 1-4, wherein: step S3 is to introduce the dilution gas into the sample piece and cool the sample piece to SiO2After the temperature required by the coating deposition is reached, TEOS vapor is introduced into the sample piece to carry out SiO2And (4) depositing a coating.
6. A TiN and silicon dioxide double-layer coating deposition device is characterized in that: comprises a CVD gas supply system, an MOCVD gas supply system and a deposition system; the CVD gas supply system and the MOCVD gas supply system are both connected to the deposition system; the deposition of TiN coating and SiO are carried out in the deposition system2Deposition of the coating, the CVD gas supply system providing TiN feed gas for the deposition system during deposition of the TiN coating in the deposition system, and the MOCVD gas supply system performing SiO deposition in the deposition system2Providing SiO to the deposition system during deposition of the coating2A raw material gas.
7. The apparatus of claim 6, wherein: the CVD gas supply system comprises N2Feed gas supply line, H2A raw gas supply pipe, a first carrier gas supply pipe, TiCl4An evaporator and a gas mixing container, wherein the output end of the first carrier gas supply pipeline is connected with TiCl4Evaporator, said N2Feed gas supply line, H2Feed gas supply line and TiCl4The output end of the evaporator is connected with a gas mixing container, and the gas mixing container is connected with a deposition system.
8. The apparatus of claim 7, wherein: the TiCl4And a first heating belt is arranged on a pipeline connecting the output end of the evaporator and the gas mixing container and a pipeline connecting the gas mixing container and the deposition system.
9. The apparatus of claim 6, wherein: the MOCVD gas supply system comprises a diluent gas supply pipeline, a second carrier gas supply pipeline and a TEOS evaporator; the output end of the second carrier gas supply pipeline is connected with the TEOS evaporator, and the output ends of the dilution gas supply pipeline and the TEOS evaporator are both connected to the deposition system.
10. The apparatus of claim 9, wherein: and a second heating belt is arranged on a pipeline for connecting the output end of the TEOS evaporator with the deposition system.
CN202111414586.2A 2021-11-25 2021-11-25 Deposition method and device for TiN and silicon dioxide double-layer coating Pending CN114150293A (en)

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