CN112941493A

CN112941493A - Device and method for pulse type uniform film rapid vapor deposition

Info

Publication number: CN112941493A
Application number: CN202110127372.0A
Authority: CN
Inventors: 冯昊; 李建国; 张王乐; 惠龙飞; 秦利军
Original assignee: Xian Modern Chemistry Research Institute
Current assignee: Xian Modern Chemistry Research Institute
Priority date: 2021-01-29
Filing date: 2021-01-29
Publication date: 2021-06-11
Anticipated expiration: 2041-01-29
Also published as: CN112941493B

Abstract

The invention discloses a device and a method for pulse type uniform film rapid vapor deposition, comprising a reaction chamber, a sampling part arranged at one end of the reaction chamber and a plurality of precursor vapor injection units arranged at the other end of the reaction chamber; the precursor vapor injection unit comprises a precursor vapor pipeline and an inert gas carrying pipeline which are converged into a main pipeline and then extend into the reaction chamber, a vacuum emptying branch communicated with the precursor vapor pipeline, an inert gas carrying emptying branch communicated with the inert gas carrying pipeline, a gas distributor positioned in the reaction chamber and connected with the end part of the main pipeline, a flow controller arranged on the inert gas carrying pipeline, valves arranged on the pipelines and the branches, and a storage tank connected with the precursor vapor pipeline. According to the invention, each precursor vapor can realize continuous or discontinuous pulse injection, and the concentration of the precursor vapor can be diluted and adjusted by inert carrier gas; the deposition speed of the film is ensured, and simultaneously, the reaction precursor can be saved to the maximum extent, the resource waste is reduced, and the environmental pollution is reduced.

Description

Device and method for pulse type uniform film rapid vapor deposition

Technical Field

The invention belongs to the field of device development and thin film material preparation, relates to a vapor film deposition technology including chemical vapor deposition and atomic layer deposition, and particularly relates to a device and a method for pulse type uniform film rapid vapor deposition.

Background

Chemical vapor deposition is a technique that utilizes one or more precursor substances in a gaseous or vapor state to decompose or react at the gas or gas-solid interface to form a solid deposit. Atomic layer deposition can be considered as one of chemical vapor deposition reactions, which achieve the controlled growth of thin films on the surface of a substrate material by two-step surface chemical reactions with self-limiting properties by alternately injecting gaseous precursors into a reactor. In a broad sense, the CVD and ALD techniques belong to the chemical vapor deposition techniques, both of which are suitable for surface modification of substrate materials with complex pore channels, trench structures and high specific surface areas, but there is a clear difference between the two techniques: unlike CVD processes, ALD processes involve a two-step surface chemistry that is self-limiting. In the ALD reaction process, a first precursor is firstly adsorbed on the surface of a substrate, after saturated adsorption is completed, unreacted precursors are removed through purging by inert carrier gas, and then a second precursor is injected to react with the first precursor to generate a target product. The self-limiting feature of the ALD reaction enables unreacted precursors to be removed after surface reaction occurs in each step, and the two precursors can be enabled to react strictly according to the stoichiometric ratio, so that the precise control of the film growth process is realized in the single atomic layer scale.

The film deposited by the ALD technology has the advantages of low deposition temperature, strong adhesion between the film and a substrate, high density and the like, but has the defect of slow film growth rate (S.M. George, Atomic layer deposition: An overview, chem.Rev.110(2010) 111-131); the CVD technology has the advantages of high deposition temperature, fast film speed, etc., but the compactness and adhesion with the substrate material are inferior to those of the film prepared by ALD (X.Wang, G.Yushi, Chemical vapor deposition and Chemical layer deposition for advanced lithium batteries and supercapacitors, Energy Environment, Sci.8(2015) 1889-1904.). The current single CVD device or ALD device is difficult to realize the injection of a plurality of precursor vapors including ALD and CVD, and cannot realize the preparation of ALD-VCD composite films with the advantages of ALD and CVD technologies. In addition, conventional CVD or ALD apparatus lack control of precursor concentration and gas distribution during thin film deposition, which in turn results in waste of precursor vapor while failing to deposit a target thin film with high uniformity over a large surface of a substrate material.

Disclosure of Invention

Aiming at the defects and shortcomings in the prior art, the invention aims to provide a device and a method for pulse type uniform film rapid vapor deposition, each precursor vapor can realize continuous pulse type injection and discontinuous pulse type injection, the concentration of the precursor vapor of each precursor vapor pulse is adjustable, the uniform deposition of a film on the surface of a sample is realized by arranging a gas distributor at the front end of the sample, and a typical ALD film deposition long mode, a typical CVD film deposition mode or a novel ALD + CVD film deposition mode is realized by controlling the injection mode and the injection time sequence of each precursor vapor.

In order to achieve the purpose, the technical scheme of the invention is as follows:

a pulse type uniform film rapid vapor deposition device comprises a reaction chamber, a sampling part arranged at one end of the reaction chamber, and a plurality of precursor vapor injection units arranged at the other end of the reaction chamber;

the precursor vapor injection unit includes: the device comprises a precursor vapor pipeline, an inert gas-carrying pipeline, a vacuum emptying branch, an inert gas-carrying emptying branch, a gas distributor, a flow controller, valves and a storage tank, wherein the precursor vapor pipeline and the inert gas-carrying pipeline are converged into a main pipeline and then extend into a reaction chamber, the vacuum emptying branch is communicated with the precursor vapor pipeline, the inert gas-carrying emptying branch is communicated with the inert gas-carrying pipeline, the gas distributor is positioned in the reaction chamber and is connected with the end part of the main pipeline, the flow controller is arranged on the inert gas-carrying pipeline, the valves are arranged.

The invention also comprises the following technical characteristics:

specifically, the plurality of precursor vapor injection units are an a precursor vapor injection unit and a B precursor vapor injection unit respectively;

the A precursor vapor injection unit includes: the device comprises a precursor steam pipeline A and an inert gas-carrying pipeline A, wherein the precursor steam pipeline A and the inert gas-carrying pipeline A are converged into a main pipeline A and then extend into a reaction chamber, a branch vacuum emptying branch A arranged on the precursor steam pipeline A, a branch inert gas-carrying emptying branch A arranged on the inert gas-carrying pipeline A, a storage tank A connected to the precursor steam pipeline A, a gas distributor A positioned in the reaction chamber and connected to the end part of the main pipeline A, a flow controller A arranged on the inert gas-carrying pipeline A, a valve AI arranged on the precursor steam pipeline A, a valve AIII arranged on the inert gas-carrying pipeline A, a valve AII arranged on the vacuum emptying branch A and a valve AIV arranged on the inert gas-carrying emptying branch A; the valve AI is positioned between the storage tank A and the valve AII, and the inert carrier gas emptying branch A is positioned between the valve AIII and the flow controller A;

the B precursor vapor injection unit includes: the device comprises a precursor steam pipeline B and an inert gas-carrying pipeline B, wherein the precursor steam pipeline B and the inert gas-carrying pipeline B are converged into a main pipeline B and then extend into a reaction chamber, a branch vacuum evacuation branch B arranged on the precursor steam pipeline B, a branch inert gas-carrying evacuation branch B arranged on the inert gas-carrying pipeline B, a storage tank B connected to the precursor steam pipeline B, a gas distributor B positioned in the reaction chamber and connected to the end part of the main pipeline B, a flow controller B arranged on the inert gas-carrying pipeline B, a valve BI arranged on the precursor steam pipeline B, a valve BIII arranged on the inert gas-carrying pipeline B, a valve BII arranged on the vacuum evacuation branch B and a valve BIV arranged on the inert gas-carrying evacuation branch B; and valve BI is located between reservoir B and valve BII, and inert carrier gas evacuation branch B is located between valve BIII and flow controller B.

Specifically, the vacuum evacuation branch A and the vacuum evacuation branch B are both connected with a vacuum pump I;

the flow rate of the gas controlled by the flow controller A and the flow controller B is 0-500 sccm; the on-off time of each valve is 0-10000 s.

Specifically, a plurality of air outlet holes are formed in the gas distributor, and the gas distributor is communicated with the main pipeline through a metal pipeline; the gas distributor is arranged close to the sample to be processed; and after the precursor steam enters the gas distributor, the precursor steam is uniformly distributed on the surface of the sample to be processed through a plurality of gas outlets.

Specifically, heating sleeves are sleeved outside the reaction chamber, the main pipeline, the precursor steam pipeline and the storage tank.

Specifically, the sampling part comprises a four-way joint, a first interface of the four-way joint is communicated with the reaction chamber in a sealing mode, a second interface of the four-way joint is connected with a vacuum pump II and is provided with a manual angle valve, a third interface of the four-way joint is a sample taking and delivering port, and a fourth interface of the four-way joint is provided with a vacuum degree sensor.

A method for pulse type uniform film rapid vapor deposition is provided, which realizes continuous pulse type injection of each precursor vapor into a reaction chamber or intermittent pulse type injection of the precursor vapor into the reaction chamber by controlling valve switches on each precursor vapor pipeline and a vacuum emptying branch;

the injection time sequence of different precursor steam pulses is realized by controlling the on-off duration of each valve on each precursor steam pipeline and each valve on the inert carrier gas pipeline;

by controlling the injection mode and the injection time sequence of each precursor steam, an ALD thin film deposition mode, a CVD thin film deposition mode and an ALD + CVD thin film deposition mode can be realized; and before each precursor steam pulse is injected into the reaction chamber, the concentration can be diluted and adjusted.

Specifically, in the ALD film deposition mode in the method, reaction precursor steam pulses are alternately injected into a reaction chamber, and an inert carrier gas purging process is inserted between the different reaction precursor steam pulses to obtain a target film with accurately controllable thickness on the surface of a sample to be processed; the method specifically comprises the following steps:

step 1: opening a valve AI, injecting precursor vapor A into the reaction chamber, wherein the injection time is t 1;

step 2: closing the valve AI, opening the valve AIII and injecting inert carrier gas to blow the precursor molecules A which are not adsorbed and physically adsorbed on the surface of the sample to be treated and the by-products generated by the surface chemical reaction away from the reaction chamber, wherein the injection time of the inert carrier gas is t 2;

and step 3: opening a valve BI, and injecting B precursor steam into the reaction chamber, wherein the injection time is t 3;

and 4, step 4: closing a valve BI, opening the valve BIII, and injecting inert carrier gas to blow B precursor molecules which are not adsorbed and physically adsorbed on the surface of the sample to be processed and byproducts generated by surface chemical reaction away from the reaction chamber, wherein the injection time of the inert carrier gas is t 4;

and (5) repeatedly executing the steps 1-4, and depositing a target film with the required thickness on the surface of the sample to be processed.

Specifically, in the CVD film deposition mode in the method, each reaction precursor steam pulse is synchronously injected into a reaction chamber, and each reaction precursor steam generates a chemical reaction in a gas phase area to generate a target product and is deposited on the surface of a sample to be processed to form a target film; the method specifically comprises the following steps:

step 1: simultaneously opening a valve AI and a valve BI, and synchronously injecting the precursor vapor A and the precursor vapor B into the reaction chamber, wherein the injection time is t 5;

step 2: after the target film rapidly grows on the surface of the sample to be processed and the required target thickness is achieved, the valve AI and the valve BI are closed at the same time, the valve AIII and the valve BIII are opened, inert carrier gas is injected, and precursor molecules which do not participate in the reaction are blown out of the reaction chamber, wherein the injection time is t 6.

Specifically, the ALD + CVD film deposition mode in the method is a precursor vapor injection mode in different precursor vapor injection modes, namely the ALD film deposition mode and the CVD film deposition mode, and different precursor vapor pulse injection sequences are partially overlapped to realize rapid vapor deposition of a uniform film, and the method specifically comprises the following steps:

step 1: opening a valve AI, injecting precursor vapor A into the reaction chamber, wherein the injection time is t7+ t 8; when the pulse injection time of the precursor vapor A into the reaction chamber reaches t7, opening a valve BI, and injecting the precursor vapor B into the reaction chamber, wherein the injection time is t 8;

step 2: closing the valve AI, keeping the valve BI in an open state, and continuously injecting the precursor steam pulse B into the reaction chamber for an injection time period t 9;

and step 3: opening a valve AIII and a valve BIII to inject inert carrier gas to blow precursor molecules which do not participate in the reaction away from the reaction chamber, wherein the injection time is t 10;

and (5) repeatedly executing the steps 1-3, and depositing a target film with the required thickness on the surface of the sample to be processed.

Compared with the prior art, the invention has the beneficial technical effects that:

1. according to the invention, continuous pulse injection and discontinuous pulse injection can be realized for each precursor vapor, and the concentration of the precursor vapor of each precursor vapor pulse can be diluted and adjusted by the bypass inert carrier gas.

2. The modularized gas distributor can realize the uniformity of the film deposition on the surfaces of various samples to be processed.

3. The invention can realize a plurality of thin film deposition thin films by controlling the injection mode and the injection time sequence of each precursor vapor, including a typical ALD thin film deposition long mode, a typical CVD thin film deposition mode or a novel ALD + CVD thin film deposition mode. The three precursor steam injection modes for film deposition can control the concentration of precursor steam by controlling the injection and dilution of bypass carrier gas, ensure the film deposition speed and simultaneously save reaction precursors to the maximum extent, reduce resource waste and reduce environmental pollution.

4. The invention can realize the preparation of the ALD-CVD composite film, fully exerts the respective advantages of the ALD technology and the CVD technology, and can realize the rapid deposition of the film while ensuring the quality of the deposited film.

Drawings

FIG. 1 is a schematic diagram showing the overall structure of the apparatus of the present invention, wherein (a) is a front view of a gas distributor, (b) is a rear view of the gas distributor, and (c) is a top view of the gas distributor.

The reference numerals have the meanings given below:

100. a reaction chamber, 201, precursor vapor lines a, 202, inert carrier gas lines a, 203, main lines a, 204, vacuum evacuation branches a, 205, inert carrier gas evacuation branches a, 206, storage tanks a, 207, gas distributors a, 208, flow controllers a, 209, valves AI, 210, valves AII, 211, valves AIII, 212, valves AIV; 301. a precursor vapor line B, 302, an inert carrier gas line B, 303, a main line B, 304, a vacuum evacuation branch B, 305, an inert carrier gas evacuation branch B, 306, a storage tank B, 307, a gas distributor B, 308, a flow controller B, 309, a valve BI, 310, a valve BII, 311, a valve BIII, 312, a valve BIV; 400. heating jacket, 500, sample to be processed; 601. vacuum pump II, 602, manual angle valve, 603, sample taking and delivering port, 604, vacuum degree sensor; 701. and a vacuum pump I.

Detailed Description

The invention provides a device and a method for pulse type uniform film rapid vapor deposition, wherein each precursor vapor can realize continuous pulse type injection and discontinuous pulse type injection, the concentration of the precursor vapor of each precursor vapor pulse is adjustable, a gas distributor is arranged at the front end of a sample to realize uniform deposition of a film on the surface of the sample, and a typical ALD film deposition long mode, a typical CVD film deposition mode or a novel ALD + CVD film deposition mode are realized by controlling the injection mode and the injection time sequence of each precursor vapor. (1) In a typical vapor injection mode of an ALD (atomic layer deposition) film deposition precursor, different precursors are alternately injected into a reaction chamber, an inert carrier gas purging process needs to be inserted, and the self-limiting surface chemical reaction of each precursor vapor on the surface of a substrate is realized to generate a target product; (2) a typical CVD film deposition precursor vapor injection mode, namely, injecting various precursor vapors into a reaction chamber at the same time to realize that the various precursor vapors complete a vapor phase chemical reaction in a vapor phase region, generate a target product and deposit the target product on the surface of a substrate; (3) and a novel ALD + CVD film deposition precursor vapor injection mode can be realized, namely the overlapping duration of different precursor vapor injection pulses is controlled, namely the target film is obtained through the chemical reaction on the surface of the substrate and the chemical reaction in a gas phase area, and the advantages of the ALD and CVD modes can be simultaneously realized in the film deposition speed and the control precision.

The invention provides a device for pulse type uniform film rapid vapor deposition, which comprises a reaction chamber 100, a sampling part arranged at one end of the reaction chamber, and a plurality of precursor vapor injection units arranged at the other end of the reaction chamber.

The precursor steam pipeline is directly communicated with the reaction chamber, and precursor steam is injected into the reaction chamber when a table valve of the precursor steam pipeline is in an open state and a valve of the vacuum emptying branch is in a closed state.

The vacuum evacuation branch is connected to the vacuum pump directly or through vacuum valve pipe fittings, when the valve of the precursor steam pipeline is in a closed state and the valve of the vacuum evacuation branch is in an open state, the redundant precursor steam on the precursor steam pipeline is evacuated, and pipeline blockage or cross contamination is avoided.

And when the valve of the inert carrier gas emptying branch is in a closed state, the inert carrier gas in the inert carrier gas pipeline is injected into the reaction chamber and dilutes and adjusts the precursor vapor injected at the same time.

The inert carrier gas emptying branch is directly communicated to the atmosphere, when the valve of the inert carrier gas emptying branch is in a closed state and the valve of the inert carrier gas emptying branch is in an open state, the inert carrier gas transmitted by the mass flow meter is emptied, and the pressure build-up in the pipeline is prevented.

In the present embodiment, more specifically, the plurality of precursor vapor injection units are an a precursor vapor injection unit and a B precursor vapor injection unit, respectively.

The a precursor vapor injection unit includes: the reaction device comprises a precursor vapor pipeline A201 and an inert carrier gas pipeline A202, wherein the precursor vapor pipeline A201 and the inert carrier gas pipeline A202 are merged into a main pipeline A203 and then extend into a reaction chamber 100, a branch vacuum evacuation branch A204 arranged on the precursor vapor pipeline A201, a branch inert carrier gas evacuation branch A205 arranged on the inert carrier gas pipeline A202, a storage tank A206 connected to the precursor vapor pipeline A201, a gas distributor A207 positioned in the reaction chamber 100 and connected to the end part of the main pipeline A203, a flow controller A208 arranged on the inert carrier gas pipeline A202, a valve AI209 arranged on the precursor vapor pipeline A201, a valve AIII211 arranged on the inert carrier gas pipeline A202, a valve AII210 arranged on the vacuum evacuation branch A204 and a valve AIV212 arranged on the inert carrier gas evacuation branch A205; and valve AI209 is located between reservoir a206 and valve AII210 and inert carrier gas evacuation branch a205 is located between valve AIII211 and flow controller a 208.

The B precursor vapor injection unit includes: the precursor vapor pipeline B301 and the inert carrier gas pipeline B302 are merged into a main pipeline B303 and then extend into the reaction chamber 100, a branch vacuum evacuation branch B304 arranged on the precursor vapor pipeline B301, a branch inert carrier gas evacuation branch B305 arranged on the inert carrier gas pipeline B302, a storage tank B306 connected to the precursor vapor pipeline B301, a gas distributor B307 positioned in the reaction chamber 100 and connected to the end part of the main pipeline B303, a flow controller B308 arranged on the inert carrier gas pipeline B302, a valve BI309 arranged on the precursor vapor pipeline B301, a valve BIII311 arranged on the inert carrier gas pipeline B302, a valve BII310 arranged on the vacuum evacuation branch B304 and a valve BIV312 arranged on the inert carrier gas evacuation branch B305; and valve BI309 is located between reservoir B306 and valve BII310 and inert carrier gas evacuation branch B305 is located between valve BIII311 and flow controller B308.

The vacuum evacuation branch A204 and the vacuum evacuation branch B304 are both connected with a vacuum pump I701; the flow rate of the gas can be controlled to be 0-500sccm by the flow controllers A208 and B308; the on-off time of each valve is 0-10000 s.

The gas distributor is provided with a plurality of gas outlet holes and is communicated with the main pipeline through a metal pipeline; the gas distributor is arranged close to the sample 500 to be processed; after entering the gas distributor, the precursor vapor is uniformly distributed on the surface of the sample 500 to be processed through a plurality of gas outlets.

The reaction chamber 100, the main pipeline, the precursor vapor pipeline and the storage tank are all externally sleeved with a heating jacket 400. Different storage tanks and reaction chambers can be heated to target temperature, corresponding temperature ranges can be set according to the temperature required by volatilization of specific reaction precursors and the temperature required by deposition of films in the reaction chambers, the temperature of the storage tanks is between room temperature and 400 ℃, and the temperature of the reaction chambers is between 60 and 1000 ℃.

The sampling part comprises a four-way joint, a first interface of the four-way joint is communicated with the reaction chamber in a sealing mode, a second interface of the four-way joint is connected with a vacuum pump II601, a manual angle valve 602 is arranged on the second interface, a third interface of the four-way joint is a sample taking and delivering port 603, and a fourth interface of the four-way joint is provided with a vacuum degree sensor 604.

The embodiment also provides a method for pulse type uniform film rapid vapor deposition, which realizes continuous pulse type injection of precursor vapor into a reaction chamber or intermittent pulse type injection of precursor vapor into the reaction chamber by controlling valve switches on precursor vapor pipelines and vacuum emptying branches; the continuous pulse type injection of the precursor vapor into the reaction chamber means that the continuous pulse type injection of the precursor vapor into the reaction chamber is realized by controlling a valve of the precursor vapor injected into the reaction chamber to be in a normally open state and a valve of a vacuum emptying branch to be in a normally closed state; the intermittent pulse type injection of the precursor vapor into the reaction chamber is realized by controlling the valve of the precursor vapor injected into the reaction chamber and the valve of the vacuum emptying branch circuit to be alternately in an open state and a closed state.

The injection time sequence of different precursor steam pulses is realized by controlling the on-off duration of each valve on each precursor steam pipeline and each valve on the inert carrier gas pipeline; the injection timing refers to the duration and sequence of injection of each precursor vapor pulse and inert carrier gas into the reaction chamber.

By controlling the injection mode and the injection time sequence of each precursor steam, an ALD thin film deposition mode, a CVD thin film deposition mode and an ALD + CVD thin film deposition mode can be realized; and before each precursor steam pulse is injected into the reaction chamber, the concentration can be diluted and adjusted. The concentration of each precursor vapor can be diluted and adjusted before being injected into the reaction chamber by pulse, that is, the precursor vapor pipeline and the inert carrier gas pipeline are synchronously opened, and the precursor vapor is injected while quantitative inert carrier gas is injected to dilute and adjust the concentration of the precursor vapor injected into the reaction chamber.

The valve can be controlled to be opened or closed through pneumatic control or electric control, and is arranged on the gas transmission pipeline and used for blocking or opening the transmission of gas in the pipeline. The inert carrier gas is nitrogen, argon or helium.

In the ALD film deposition mode in the method, reaction precursor steam pulses are alternately injected into a reaction chamber, and inert carrier gas purging processes are inserted between the different reaction precursor steam pulses to obtain a target film with accurately controllable thickness on the surface of a sample to be processed; the method specifically comprises the following steps:

In the CVD film deposition mode in the method, each reaction precursor steam pulse is synchronously injected into a reaction chamber, and each reaction precursor steam generates a chemical reaction in a gas phase area to generate a target product and is deposited on the surface of a sample to be processed to form a target film; the method specifically comprises the following steps:

The ALD and CVD film deposition mode in the method is a precursor steam injection mode in different precursor steam injection modes, and has the ALD film deposition mode and the CVD film deposition mode, different precursor steam pulse injection sequences are partially overlapped, and the rapid vapor deposition of uniform films is realized, and the method specifically comprises the following steps:

The present invention is not limited to the following embodiments, and all equivalent changes based on the technical solutions of the present invention fall within the protection scope of the present invention.

Example 1:

this example shows an apparatus and method for pulsed ALD of uniform thin film vapor deposition of ZnO, the apparatus used in the example is shown in FIG. 1. The prepared film is ZnO, and the two precursors are Zn (C)₂H₅)₂And H₂And O is respectively arranged in a storage tank A and a storage tank B, the storage tank A and the storage tank B are at room temperature, and the flow rates of the mass flow meters of the bypass inert carrier gas purging main pipeline of the two storage tanks are set to be 50 sccm. The substrate material is silicon wafer, and the inert carrier gas is N₂The temperature for the atomic layer deposition experiment was 110 ℃. And setting all odd-numbered valves to be in a closed state before being triggered and setting all even-numbered valves to be in an open state before being triggered by a program.

The method specifically comprises the following steps:

step 1: opening valve AI, closing valve AII, opening valve AIII, closing valve AIV, keeping other valves in default state, and diluting Zn (C) with inert carrier gas₂H₅)₂Steam is injected into the reaction chamber through the gas distributor, and the injection time is 5.0 s;

step 2: opening a valve AIII, closing a valve AIV, opening a valve BIII, closing a valve BIV, keeping other valves in a default state, injecting inert carrier gas into the reaction cavity to clean physical adsorption, byproducts and the like on the surface of the silicon wafer, wherein the injection time of the inert carrier gas is 10.0 s;

and step 3: opening valve BI, closing valve BII, opening valve BIII, closing valve BIV, keeping other valves in default state, and diluting with inert carrier gas₂Injecting O steam into the reaction chamber through a gas distributor for 5.0 s;

and 4, step 4: opening a valve AIII, closing a valve AIV, opening a valve BIII, closing a valve BIV, keeping other valves in a default state, injecting inert carrier gas into the reaction cavity to clean physical adsorption, byproducts and the like on the surface of the silicon wafer, wherein the injection time of the inert carrier gas is 10.0 s;

and repeating the steps 1-4200 times to deposit the target film with the required thickness on the surface of the silicon wafer.

Example 2:

this example shows an apparatus and method for pulsed CVD ZnO uniform thin film vapor deposition, the apparatus used in the example is shown in FIG. 1. The prepared film is ZnO, and the two precursors are Zn (C)₂H₅)₂And H₂And O is respectively arranged in a storage tank A and a storage tank B, the storage tank A and the storage tank B are at room temperature, and the flow rates of the mass flow meters of the bypass inert carrier gas purging main pipeline of the two storage tanks are set to be 50 sccm. The substrate material is silicon wafer, and the inert carrier gas is N₂Chemical gasThe phase deposition experiment temperature was 450 ℃. And setting all odd-numbered valves to be in a closed state before being triggered and setting all even-numbered valves to be in an open state before being triggered by a program.

The method specifically comprises the following steps:

step 1: opening valve AI, closing valve AII, opening valve BI, closing valve BII, opening valve AIII, closing valve AIV, opening valve BIII, closing valve BIV, and diluting Zn (C) with inert carrier gas₂H₅)₂Steam and H2O steam are injected into the reaction chamber through the gas distributor at the same time, and the injection time is 1000.0 s;

step 2: opening a valve AIII, closing a valve AIV, opening a valve BIII, closing a valve BIV, keeping other valves in a default state, injecting inert carrier gas into the reaction cavity to clean physical adsorption, byproducts and the like on the surface of the silicon wafer, wherein the injection time of the inert carrier gas is 100.0 s;

and (3) depositing a target film with the required thickness on the surface of the silicon wafer, and changing the continuous injection time of the two precursors in the step (1) according to the requirement on the film thickness.

Example 3:

this example shows an apparatus and method for pulsed ALD + CVD ZnO uniform thin film rapid vapor deposition, the apparatus used in the example is shown in FIG. 1. The prepared film is ZnO, and the two precursors are Zn (C)₂H₅)₂And H₂And O is respectively arranged in a storage tank A and a storage tank B, the storage tank A and the storage tank B are at room temperature, and the flow rates of the mass flow meters of the bypass inert carrier gas purging main pipeline of the two storage tanks are set to be 50 sccm. The substrate material is silicon wafer, and the inert carrier gas is N₂The silicon wafer is in an environment with the temperature of 250 ℃. And setting all odd-numbered valves to be in a closed state before being triggered and setting all even-numbered valves to be in an open state before being triggered by a program.

The method specifically comprises the following steps:

step 1: opening valve AI, closing valve AII, opening valve AIII, closing valve AIV, keeping other valves in default state, and diluting Zn (C) with inert carrier gas₂H₅)₂Steam is injected into the reaction chamber through the gas distributor, and the injection time is 10.0 s; wherein Zn (C) after dilution with an inert carrier gas₂H₅)₂When the duration of steam pulse injection into the reaction chamber reaches 5.0s, opening the valve BI, closing the valve BII, opening the valve BIII, closing the valve BIV, and diluting Zn (C) with inert carrier gas₂H₅)₂Steam and H₂Injecting O steam into the reaction chamber through the gas distributor at the same time, wherein the injection time is 5.0 s;

step 2: opening valve BI, closing valve BII, opening valve BIII, closing valve BIV, keeping other valves in default state, and diluting with inert carrier gas₂Injecting O steam into the reaction chamber through a gas distributor for 10.0 s;

and step 3: opening a valve AIII, closing a valve AIV, opening a valve BIII, closing a valve BIV, keeping other valves in a default state, injecting inert carrier gas into the reaction cavity to clean physical adsorption, byproducts and the like on the surface of the silicon wafer, wherein the injection time of the inert carrier gas is 20.0 s;

and repeating the steps 1-3100 times, and depositing a target film with the required thickness on the surface of the silicon wafer.

Example 4:

this example presents a pulsed ALD TiO₂An apparatus and method for uniform thin film vapor deposition, the apparatus used in the example is shown in FIG. 1. The prepared film is TiO₂The two precursors used are respectively Ti (OC)₃H₇)₄And H₂O₂The inert carrier gas purging main pipeline is respectively arranged in a storage tank A and a storage tank B, the storage tank A is heated to 60 ℃, the storage tank B is at room temperature, and the flow rates of mass flowmeters of the bypass inert carrier gas purging main pipeline of the two storage tanks are set to be 40 sccm. The substrate material is a silicon wafer, the inert carrier gas is Ar, and the experimental temperature of atomic layer deposition is 150 ℃. And setting all odd-numbered valves to be in a closed state before being triggered and setting all even-numbered valves to be in an open state before being triggered by a program.

The method specifically comprises the following steps:

step 1: opening valve AI, closing valve AII, openingValve AIII, valve AIV closed, other valves default state, Ti (OC) diluted by inert carrier gas₃H₇)₄Steam is injected into the reaction chamber through the gas distributor, and the injection time is 10.0 s;

step 2: opening a valve AIII, closing a valve AIV, opening a valve BIII, closing a valve BIV, keeping other valves in a default state, injecting inert carrier gas into the reaction cavity to clean physical adsorption, byproducts and the like on the surface of the silicon wafer, wherein the injection time of the inert carrier gas is 20.0 s;

and step 3: opening valve BI, closing valve BII, opening valve BIII, closing valve BIV, keeping other valves in default state, and diluting with inert carrier gas₂O₂Steam is injected into the reaction chamber through the gas distributor, and the injection time is 10.0 s;

and 4, step 4: opening a valve AIII, closing a valve AIV, opening a valve BIII, closing a valve BIV, keeping other valves in a default state, injecting inert carrier gas into the reaction cavity to clean physical adsorption, byproducts and the like on the surface of the silicon wafer, wherein the injection time of the inert carrier gas is 20.0 s;

repeating the step 1-4300 times to deposit TiO with required thickness on the surface of the silicon wafer₂A target film.

Example 5:

this example shows a pulsed CVD TiO₂An apparatus and method for uniform thin film vapor deposition, the apparatus used in the example is shown in FIG. 1. The prepared film is TiO₂The two precursors used are respectively Ti (OC)₃H₇)₄And H₂O₂The inert carrier gas purging main pipeline is respectively arranged in a storage tank A and a storage tank B, the storage tank A is heated to 60 ℃, the storage tank B is at room temperature, and the flow rates of mass flowmeters of the bypass inert carrier gas purging main pipeline of the two storage tanks are set to be 40 sccm. The substrate material is a silicon wafer, the inert carrier gas is Ar, and the experimental temperature of atomic layer deposition is 150 ℃. And setting all odd-numbered valves to be in a closed state before being triggered and setting all even-numbered valves to be in an open state before being triggered by a program.

The method specifically comprises the following steps:

step 1: opening valve AI, closing valve AII, opening valve BI, closing valve BII, opening valve AIII, closing valve AIV, opening valve BIII, closing valve BIV, and diluting Ti (OC) with inert carrier gas₃H₇)₄Steam and H₂O₂Steam is injected into the reaction chamber through the gas distributor at the same time, and the injection time is 2000.0 s;

step 2: opening a valve AIII, closing a valve AIV, opening a valve BIII, closing a valve BIV, keeping other valves in a default state, injecting inert carrier gas into the reaction cavity to clean physical adsorption, byproducts and the like on the surface of the silicon wafer, wherein the injection time of the inert carrier gas is 300.0 s;

Example 6:

this example shows an apparatus and method for pulsed ALD + CVD TiO2 uniform thin film rapid vapor deposition, the apparatus used in the example is shown in FIG. 1. The prepared film is TiO₂The two precursors used are respectively Ti (OC)₃H₇)₄And H₂O₂The inert carrier gas purging main pipeline is respectively arranged in a storage tank A and a storage tank B, the storage tank A is heated to 60 ℃, the storage tank B is at room temperature, and the flow rates of mass flowmeters of the bypass inert carrier gas purging main pipeline of the two storage tanks are set to be 40 sccm. The substrate material is a silicon wafer, the inert carrier gas is Ar, and the experimental temperature of atomic layer deposition is 150 ℃. And setting all odd-numbered valves to be in a closed state before being triggered and setting all even-numbered valves to be in an open state before being triggered by a program.

The method specifically comprises the following steps:

step 1: opening valve AI, closing valve AII, opening valve AIII, closing valve AIV, keeping other valves in default state, and diluting Zn (C) with inert carrier gas₂H₅)₂Steam is injected into the reaction chamber through the gas distributor, and the injection time is 10.0 s; wherein Zn (C) after dilution with an inert carrier gas₂H₅)₂When steam is injected into the reaction chamberOpening valve BI, closing valve BII, opening valve BIII, closing valve BIV, diluting Ti (OC) with inert carrier gas when the length reaches 5.0s₃H₇)₄Steam and H₂O₂Steam is injected into the reaction chamber through the gas distributor at the same time, and the injection time is 5.0 s;

step 2: opening valve BI, closing valve BII, opening valve BIII, closing valve BIV, keeping other valves in default state, and diluting with inert carrier gas₂O₂Steam is injected into the reaction chamber through the gas distributor, and the injection time is 10.0 s;

and repeating the step 1-3200 times, and depositing a target film with the required thickness on the surface of the silicon wafer.

Claims

1. The device for pulse type uniform film rapid vapor deposition is characterized by comprising a reaction chamber (100), a sampling part arranged at one end of the reaction chamber, and a plurality of precursor vapor injection units arranged at the other end of the reaction chamber;

2. The apparatus of claim 1, wherein the plurality of precursor vapor injection units are an a precursor vapor injection unit and a B precursor vapor injection unit, respectively;

the A precursor vapor injection unit includes: a precursor vapor pipeline A (201) and an inert carrier gas pipeline A (202) which are merged into a main pipeline A (203) and then extend into the reaction chamber (100), a branch vacuum evacuation branch A (204) arranged on the precursor vapor pipeline A (201), a branch inert carrier gas evacuation branch A (205) arranged on the inert carrier gas pipeline A (202), a storage tank A (206) connected with the precursor vapor pipeline A (201), and a gas distributor A (207) positioned in the reaction chamber (100) and connected with the end part of the main pipeline A (203), a flow controller A (208) arranged on the inert carrier gas pipeline A (202), a valve AI (209) arranged on the precursor vapor pipeline A (201), a valve AIII (211) arranged on the inert carrier gas pipeline A (202), a valve AII (210) arranged on the vacuum emptying branch A (204) and a valve AIV (212) arranged on the inert carrier gas emptying branch A (205); and valve AI (209) is located between reservoir A (206) and valve AII (210), and inert carrier gas evacuation branch A (205) is located between valve AIII (211) and flow controller A (208);

the B precursor vapor injection unit includes: a precursor vapor pipeline B (301) and an inert carrier gas pipeline B (302) which are merged into a main pipeline B (303) and then extend into the reaction chamber (100), a branch vacuum emptying branch B (304) arranged on the precursor vapor pipeline B (301), a branch inert carrier gas emptying branch B (305) arranged on the inert carrier gas pipeline B (302), a storage tank B (306) connected with the precursor vapor pipeline B (301), and a gas distributor B (307) positioned in the reaction chamber (100) and connected with the end part of the main pipeline B (303), a flow controller B (308) arranged on the inert carrier gas pipeline B (302), a valve BI (309) arranged on the precursor vapor pipeline B (301), a valve BIII (311) arranged on the inert carrier gas pipeline B (302), a valve BII (310) arranged on the vacuum evacuation branch B (304) and a valve BIV (312) arranged on the inert carrier gas evacuation branch B (305); and valve BI (309) is located between reservoir B (306) and valve BII (310), and inert carrier gas evacuation branch B (305) is located between valve BIII (311) and flow controller B (308).

3. The apparatus according to claim 2, wherein the vacuum evacuation branch a (204) and the vacuum evacuation branch B (304) are connected to a vacuum pump I (701);

the flow rate of the controllable gas of the flow controller A (208) and the flow controller B (308) is 0-500 sccm; the on-off time of each valve is 0-10000 s.

4. The apparatus according to claim 1, wherein the gas distributor has a plurality of gas outlets, and the gas distributor is connected to the main pipeline via metal pipes; the gas distributor is arranged close to the sample (500) to be processed; the precursor vapor enters the gas distributor and then is uniformly distributed on the surface of the sample (500) to be processed through a plurality of gas outlets.

5. The apparatus according to claim 1, wherein the reaction chamber (100), the main line, the precursor vapor line, and the storage tank are all covered with a heating jacket (400).

6. The apparatus according to claim 1, wherein the sampling unit comprises a four-way joint, a first port of the four-way joint is in sealed communication with the reaction chamber, a second port of the four-way joint is connected with a vacuum pump II (601) and is provided with a manual angle valve (602), a third port of the four-way joint is a sample feeding port (603), and a fourth port of the four-way joint is provided with a vacuum degree sensor (604).

7. A method for pulse type uniform film rapid vapor deposition is characterized in that the method realizes continuous pulse type injection of precursor vapor into a reaction chamber or discontinuous pulse type injection of precursor vapor into the reaction chamber by controlling valve switches on precursor vapor pipelines and vacuum emptying branches;

8. The method of claim 7, wherein the ALD film deposition mode is an alternate reactive precursor vapor pulse injection into the reaction chamber, and an inert carrier gas purge is inserted between different reactive precursor vapor pulse injections to obtain a target film with a precisely controllable thickness on the surface of the sample to be processed; the method specifically comprises the following steps:

9. The method of claim 7, wherein the CVD film deposition mode is a CVD film deposition mode in which each reactive precursor vapor pulse is injected into the reaction chamber simultaneously, and each reactive precursor vapor undergoes a chemical reaction in the vapor phase region to form a target product and is deposited on the surface of the sample to be processed to form a target film; the method specifically comprises the following steps:

10. The method of claim 7, wherein the ALD + CVD film deposition mode is one of different precursor vapor injection modes, and the ALD film deposition mode and the CVD film deposition mode have the precursor vapor injection modes, and the pulse injection sequences of different precursor vapors partially overlap to achieve the rapid vapor deposition of the uniform film, the method comprising the steps of: