CN107460450B - Device for preparing component-gradient bismuth aluminum gallium oxide film - Google Patents

Device for preparing component-gradient bismuth aluminum gallium oxide film Download PDF

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CN107460450B
CN107460450B CN201710579317.9A CN201710579317A CN107460450B CN 107460450 B CN107460450 B CN 107460450B CN 201710579317 A CN201710579317 A CN 201710579317A CN 107460450 B CN107460450 B CN 107460450B
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pipeline
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source gas
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CN107460450A (en
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王志亮
宋长青
尹海宏
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Nantong University Technology Transfer Center Co ltd
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Nantong University
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Abstract

Bi (Al) with gradually changed componentsxGa1‑x)O3The thin film material is obtained by adopting self-limiting surface adsorption reaction. In each growth period controlled by the program, two counters are provided for setting and controlling the number of pulses of the organoaluminum source gas and the organogallium source gas in each growth period, respectively, and in the successive growth process, the value of one of the counters is gradually increased and the value of the other counter is gradually decreased. Production of Bi (Al) by Using the apparatus of the present inventionxGa1‑x)O3The method of the film material can realize the Bi (Al) with gradually changed components and crossing the morphotropic phase boundaryxGa1‑x)O3A thin film material, and Bi (Al)xGa1‑x)O3The growth thickness of the film is accurately controllable.

Description

Device for preparing component-gradient bismuth aluminum gallium oxide film
Technical Field
The invention relates to a preparation device of a bismuth-based oxide thin film material, in particular to a Bi (Al)xGa1-x)O3A device for preparing ferroelectric film material.
Background
The invention is a divisional application with application number CN 201510764503.0.
Pb(Zr1-xTix)O3It is a ferroelectric and piezoelectric material with excellent performance.
However, since PZT contains lead, it is easy to cause environmental pollution during its production and use.
In the laws of many countries in europe and america, it has been clearly stated that the use of electronic components containing lead is restricted or prohibited, which greatly affects the use of PZT.
In recent years, Baettig has theoretically predicted Bi (Al)xGa1-x)O3(bismuth Algalinate, abbreviated as BAG) has a structure similar to that of Pb (Zr)1-xTix)O3The BAG is lead-free, so that the BAG becomes PZTA potential replacement.
BiGaO at room temperature3The space group of (bismuth gallate, BGO for short) is Pcca, BiAlO3The space group of (bismuth aluminate, abbreviated as BAO) is R3c, when BGO and BAO form solid solution Bi (Al) according to a certain proportionxGa1-x)O3Quasi-morphotropic phase boundaries similar to PZT materials are also formed.
However, there is no mature Bi (Al) yetxGa1-x)O3Preparation technology of materials.
Disclosure of Invention
In order to solve the problems of the prior art, the invention aims to provide a method for preparing Bi (Al) with gradually changed componentsxGa1-x)O3A thin film material.
The specific technical scheme for realizing the aim of the invention is as follows:
bi (Al)xGa1-x)O3The preparation method of the thin film material adopts an organic bismuth source, an oxygen precursor gas, an organic aluminum source and an organic gallium source gas as raw materials.
The Bi (Al)xGa1-x)O3The preparation method of the film material is completed by adopting a specially designed device.
Such devices include, but are not limited to: an organic bismuth source container 1, an organic bismuth source pipeline manual valve K1, an organic bismuth source pipeline automatic valve AK1, an organic bismuth source gas-carrying pipeline mass flow controller MFC1, an organic aluminum source gas container 2, an organic aluminum source gas pipeline manual valve K2, an organic aluminum source gas pipeline automatic valve AK2, an organic aluminum source gas-carrying pipeline mass flow controller MFC2, an organic gallium aluminum source container 3, an organic gallium source gas pipeline manual valve K3, an organic gallium source gas pipeline automatic valve AK3, an organic gallium source gas-carrying pipeline mass flow controller MFC3, an oxygen precursor gas source container 4, an oxygen precursor gas pipeline manual valve K4, an oxygen precursor gas pipeline automatic valve AK4, an oxygen precursor gas-carrying pipeline mass flow controller MFC4, an inert gas container 5, an inert gas pipeline manual valve K5, a vacuum reaction cavity, a vacuum gauge, a vacuum pump, an automatic vacuum pump inlet valve AK5, a vacuum pump, The device controller is provided with an electric heater and a temperature sensor in the vacuum reaction cavity and can be composed of a PLC (programmable logic controller), an FPGA (field programmable gate array), a CPLD (complex programmable logic device), a singlechip system, a computer or a specially designed circuit system; the organic bismuth source container 1, the organic aluminum source gas container 2 and the oxygen precursor gas source container 3 are all provided with an electric heater and a semiconductor refrigerator;
the outlet of the organic bismuth source container 1 is sequentially connected with an organic bismuth source pipeline manual valve K1, an organic bismuth source pipeline automatic valve AK1 and a vacuum reaction cavity through a gas pipeline, the outlet of the organic aluminum source gas container 2 is sequentially connected with an organic aluminum source gas pipeline manual valve K2, an organic aluminum source gas pipeline automatic valve AK2 and a vacuum reaction cavity through a gas pipeline, the outlet of the organic gallium source gas container 3 is sequentially connected with an organic gallium source gas pipeline manual valve K3, an organic gallium source gas pipeline automatic valve AK3 and a vacuum reaction cavity through a gas pipeline, the outlet of the oxygen precursor gas source container 4 is sequentially connected with an oxygen precursor gas pipeline manual valve K4, an oxygen precursor gas pipeline automatic valve AK4 and a vacuum reaction cavity through a gas pipeline, the outlet of the inert gas container 5 is connected with an inert gas pipeline manual valve K5 through a gas pipeline and is respectively connected with an organic bismuth source carrier gas pipeline mass flow controller MFC1 and MFC, An organic aluminum source gas carrier pipeline mass flow controller MFC2, an organic gallium source gas carrier pipeline mass flow controller MFC3 and an oxygen precursor gas carrier pipeline mass flow controller MFC4, wherein the outlet of the organic bismuth source gas carrier pipeline mass flow controller MFC1 is connected with a gas pipeline between an organic bismuth source pipeline automatic valve AK1 and a vacuum reaction cavity through a three-way connecting piece, the outlet of the organic aluminum source gas carrier pipeline mass flow controller MFC2 is connected with a gas pipeline between an organic aluminum source gas pipeline automatic valve AK2 and the vacuum reaction cavity through a three-way connecting piece, the outlet of the organic gallium source gas carrier pipeline mass flow controller 3 is connected with a gas pipeline between the organic aluminum source gas pipeline automatic valve AK3 and the vacuum reaction cavity through a three-way connecting piece, the outlet of the oxygen precursor gas carrier pipeline mass flow controller MFC4 is connected with a gas pipeline between the organic bismuth source pipeline automatic valve AK4 and the vacuum reaction cavity through a three-way connecting piece, the outlet of the vacuum reaction cavity is sequentially connected to an automatic valve AK5 of the vacuum pump air inlet and the air inlet of the vacuum pump through pipelines;
a vacuum gauge is arranged in the vacuum cavity;
the organic bismuth source pipeline manual valve K1, the organic aluminum source gas pipeline manual valve K2, the organic gallium source gas pipeline manual valve K3, the oxygen precursor gas pipeline manual valve K4 and the inert gas pipeline manual valve K5 are all manually opened by operators and are controlled by an uncontrolled device, and the design can ensure safety;
a vacuum gauge, an automatic valve AK1 of an organic bismuth source pipeline, a mass flow controller MFC1 of an organic bismuth source gas-carrying pipeline, an automatic valve AK2 of an organic aluminum source pipeline, an automatic valve MFC2 of an organic aluminum source gas-carrying pipeline, an automatic valve AK3 of an organic gallium source gas-carrying pipeline, a mass flow controller MFC3 of an organic gallium source gas-carrying pipeline, an oxygen precursor gas source container 4, an automatic valve AK4 of an oxygen precursor gas-carrying pipeline, an oxygen precursor gas-carrying pipeline mass flow controller MFC4, a vacuum reaction chamber, a vacuum pump, an automatic valve AK5 of a vacuum pump air inlet, an electric heater and a temperature sensor in the vacuum reaction chamber, the organic bismuth source container 1, the organic aluminum source gas container 2, the organic gallium source gas container 3, an electric heater and a semiconductor refrigerator of the oxygen gas source container 4 are all connected to the equipment controller, the device controller controls the working states of the devices in a centralized manner;
at any moment, the equipment controller controls to enable at most one of an automatic valve AK1 of the organic bismuth source pipeline, an automatic valve AK2 of the organic aluminum source gas pipeline, an automatic valve AK3 of the organic gallium source gas pipeline and an automatic valve AK4 of the oxygen precursor gas pipeline to be in an open state, and the rest of the valves are in a closed state; or the automatic valve AK1 for organic bismuth source pipeline, the automatic valve AK2 for organic aluminum source gas pipeline, the automatic valve AK3 for organic gallium source gas pipeline and the automatic valve AK4 for oxygen precursor gas pipeline are all in a closed state;
the data collected by the temperature sensor is transmitted to the equipment controller through a cable so as to realize PID control (proportional-integral-derivative control) of the temperature, and the temperature of the vacuum reaction cavity can quickly and accurately reach a set temperature value;
the working states of the electric heaters and the semiconductor refrigerator of the organic bismuth source container 1, the organic aluminum source gas container 2, the organic gallium source gas container 3 and the oxygen precursor gas source container 4 are controlled by the equipment controller, so that the temperatures of the organic bismuth source container 1, the organic aluminum source gas container 2, the organic gallium source container 3 and the oxygen precursor gas source container 4 can be kept at the set temperature values;
the Bi (Al)xGa1-x)O3The preparation method of the film material comprises the following specific steps:
A) filling inert gas into the vacuum glove box, and completing the following operations in the inert gas atmosphere of the glove box: respectively filling an organic bismuth source, an organic aluminum source gas and an organic gallium source gas into an organic bismuth source container 1, an organic aluminum source gas container 2 and an organic gallium source gas container 3, and then installing and connecting the organic bismuth source, the organic aluminum source gas and the organic gallium source gas with respective pipelines;
because the organic bismuth source, the organic aluminum source gas and the organic gallium source gas are flammable and explosive dangerous goods, the vacuum glove box is indispensable in the filling process;
B) respectively filling an oxygen precursor gas source and inert gas into an oxygen precursor gas source container 3 and an inert gas container 4, and then installing and connecting the oxygen precursor gas source and the inert gas with respective pipelines;
C) drying the cleaned substrate material by inert gas, and placing the substrate material into a substrate tray;
D) the tray and the substrate are moved into a vacuum reaction cavity, a vacuum pump is started through an equipment controller, then an automatic valve AK5 of an air inlet of the vacuum pump is opened, and the vacuum reaction cavity is vacuumized;
E) the temperature of the organic bismuth source container 1, the organic aluminum source gas container 2, the organic gallium source gas container 3 and the oxygen precursor gas source container 4 is set on the equipment controller, the equipment controller controls the working state of the electric heater and/or the semiconductor refrigerator of the organic bismuth source container 1, the organic aluminum source gas container 2, the organic gallium source gas container 3 and the oxygen precursor source container 4, the temperature of the organic bismuth source container 1, the organic aluminum source gas container 2, the organic gallium source gas container 3 and the oxygen precursor gas source container 4 is maintained at a set temperature value, so that the vapor pressure of the organic bismuth source container 1, the organic aluminum source gas container 2, the organic gallium source gas container 3 and the oxygen precursor gas source container 4 is greater than the pressure in a gas pipeline after the inert gas container 5 passes through the mass flow controllers MFC1, MFC2, MFC3 and MFC4 at the set temperature value of each precursor;
the device controller controls the electric heater to heat the vacuum cavity, so that the temperature of the tray and the substrate in the vacuum cavity is constant at a temperature value in the whole film growth process, and the temperature value is in a proper temperature window;
the suitable temperature window is: in a suitable temperature range, i.e. where the temperature of the substrate is higher than a lower temperature limit and lower than an upper temperature limit, and the flow rate of the precursor gas supply is greater than the lower limit, the growth rate of the thin film is a substantially constant value, and the growth rate of the thin film is substantially independent of the flow rate of the precursor gas supply, the flow rate of the carrier gas, i.e. the inert gas, the temperature of the precursor, the temperature of the substrate, and the degree of vacuum of the separation space of the vacuum chamber, where "substantially independent" means: even if the growth rate of the film fluctuates slightly in the temperature window, when the growth temperature exceeds the temperature window, namely is lower than the lower temperature limit or higher than the upper temperature limit, the growth rate of the film can be obviously increased or reduced;
within the temperature window, the deposition rate does not change with temperature; when the temperature is not high enough, the precursor is condensed to cause multilayer adsorption, so that the deposition rate is too high, or the adsorption is incomplete and the reaction activity is poor; precursor decomposition at too high a temperature results in additional CVD-type growth, or desorption of the precursor due to too high thermal kinetic energy; these factors all result in a significant increase or decrease in the growth rate of the film;
F) after the temperature of the vacuum cavity is constant for a period of time, the temperature is usually 5-30 minutes, and the cycle number of film growth, the gas flow rate of an organic bismuth source gas-carrying pipeline, the gas flow rate of an organic aluminum source gas-carrying pipeline, the gas flow rate of an organic gallium source gas-carrying pipeline, the gas flow rate of an oxygen precursor gas-carrying pipeline, the flow rate of an inert gas, the pulse length of an organic bismuth source gas, the pulse length of an organic aluminum source gas, the pulse length of an organic gallium source gas, the pulse length of an oxygen precursor gas and the pulse length of the inert gas are set on an equipment controller; manually opening an organic bismuth source pipeline manual valve K1, an organic aluminum source gas pipeline manual valve K2, an organic gallium source gas pipeline manual valve K3, an oxygen precursor gas pipeline manual valve K4 and an inert gas pipeline manual valve K5;
G) controlling an organic bismuth source gas-carrying pipeline mass flow controller MFC1, an organic aluminum source gas-carrying pipeline mass flow controller MFC2, an organic gallium source gas-carrying pipeline mass flow controller MFC3 and an oxygen precursor gas-carrying pipeline mass flow controller MFC4 by an equipment controller, so that the gas in each gas pipeline is introduced into a vacuum reaction cavity according to the set value in the step F), and the inert gas, the organic bismuth source gas, the organic gallium source gas, the oxygen precursor gas and the organic aluminum source gas are respectively introduced into the vacuum reaction cavity according to a certain gas pulse time sequence; all precursor gases are respectively transported by inert gases;
to realize the growth of BiGaO3Realizing Al doping in the process of film to obtain Bi (Al)xGa1-x)O3The film is formed by alternately mixing and inserting organic gallium source gas pulses and organic aluminum source gas pulses in a gas pulse sequence according to a certain proportion in each growth period, wherein the organic gallium source gas pulses and the organic aluminum source gas pulses have the desired Bi (Al) ratioxGa1-x)O3The components of the film, the adopted organic gallium source gas and the organic aluminum source gas are determined;
for example, to obtain Bi (Al)0.1Ga0.9)O3When the organic gallium source gas and the organic aluminum source gas respectively adopt triethyl gallium and triethyl aluminum, the number ratio of the organic gallium source gas pulse to the organic aluminum source gas pulse can be set to be 9:1 in one growth period.
It is to be noted in particular that: the ratio of the number of pulses of the organogallium source gas to the number of pulses of the organoaluminum source gas is not directly equal to (1-x): x, but depends on which of the organogallium source gas and the organoaluminum source gas is used.
H) When the number of the film growth cycles reaches the set number, the thickness of the filmReaching the required value to obtain Bi (Al) with certain thicknessxGa1-x)O3The thin film material is prepared by closing an organic bismuth source pipeline automatic valve AK1, an organic aluminum source gas pipeline automatic valve AK2, an organic gallium source gas pipeline automatic valve AK3 and an oxygen precursor gas pipeline automatic valve AK3 by an equipment controller, stopping introducing the organic bismuth source, the organic aluminum source gas, the organic gallium source gas and the oxygen precursor gas, continuing introducing inert gas, stopping supplying power to the electric heater and stopping heating the vacuum cavity;
I) manually closing an organic bismuth source pipeline manual valve K1, an organic aluminum source gas pipeline manual valve K2, an organic gallium source gas pipeline manual valve K3, an oxygen precursor gas pipeline manual valve K4, an inert gas pipeline manual valve K5 and a vacuum pump air inlet automatic valve AK4 to keep an open state, and naturally cooling a vacuum reaction cavity;
J) when the vacuum cavity reaches or approaches to the room temperature, the automatic valve AK5 of the vacuum pump air inlet is closed by the equipment controller;
K) inflating the vacuum reaction cavity to make the air pressure of the vacuum reaction cavity reach one atmospheric pressure, and the air pressure inside and outside the vacuum reaction cavity reach a balanced state;
l) taking out the deposit to obtain Bi (Al)xGa1-x)O3A substrate made of a thin film material, and a manual valve K5 of the inert gas pipeline is closed;
m) attaching Bi (Al) obtained in the step LxGa1-x)O3Putting a substrate of a film material into a rapid annealing furnace, performing rapid thermal annealing treatment, naturally cooling, taking out, and testing to confirm that the obtained Bi (Al) isxGa1-x)O3The space group of the film material is Pcca;
the rapid thermal annealing comprises the following steps:
(a) maintaining at 180 ℃ and 220 ℃ for 1-10 minutes;
(b) maintaining at 360-400 deg.c for 1-10 min;
(c) annealing at 750-1050 deg.c for 1-10 min;
in order to avoid the unpredictable effect of the moisture-containing air in the lines on the film growth, there should generally be an operation after step B) of expelling the air from the lines after the respective raw material container is mounted in connection therewith, specifically:
keeping the organic bismuth source pipeline manual valve K1, the organic aluminum source gas pipeline manual valve K2, the organic gallium source gas pipeline manual valve K3 and the oxygen precursor pipeline manual valve K4 in a closed state, then,
the automatic valve AK5 of the vacuum pump air inlet is controlled to be in an open state by the equipment controller, and the automatic valve AK1 of the organic bismuth source pipeline, the automatic valve AK2 of the organic aluminum source gas pipeline, the automatic valve AK3 of the organic gallium source gas pipeline and the automatic valve AK4 of the oxygen precursor gas pipeline are controlled to be in an open state by the equipment controller; when a vacuum gauge in the vacuum reaction cavity is not changed any more, the automatic valve AK5 of the vacuum pump air inlet is controlled to be in a closed state by the equipment controller, and the quality flow controller MFC1 of the organic bismuth source gas-carrying pipeline, the quality flow controller MFC2 of the organic aluminum source gas-carrying pipeline, the quality flow controller MFC3 of the organic gallium source gas-carrying pipeline and the quality flow controller MFC4 of the oxygen precursor gas-carrying pipeline are controlled by the equipment controller, so that inert gas in each gas pipeline is introduced into the vacuum reaction cavity according to a certain value; when the air pressure in the vacuum reaction cavity reaches 0.5 atmospheric pressure, the automatic valve AK5 of the air inlet of the vacuum pump is controlled to be in an open state by the equipment controller again, and the automatic valve AK1 of the organic bismuth source pipeline, the automatic valve AK2 of the organic aluminum source pipeline, the automatic valve AK3 of the organic gallium source gas pipeline and the automatic valve AK4 of the oxygen precursor gas pipeline are controlled to be in an open state by the equipment controller; repeating the above process for 3-6 times.
In step G), the gas pulse sequence is composed of an inert gas pulse, an organobismuth source gas pulse, an organogallium source gas pulse, an oxygen precursor gas pulse, and an organoaluminium source gas pulse, and if N, B, O, A, G represents the inert gas pulse, the organobismuth source gas pulse, the oxygen precursor gas pulse, the organoaluminium source gas pulse, and the organogallium source gas pulse, respectively, then:
the pulse N is realized by the following actions:
controlling an automatic valve AK1 of an organic bismuth source pipeline, an automatic valve AK2 of an organic aluminum source gas pipeline, an automatic valve AK3 of an organic gallium source gas pipeline and an automatic valve AK4 of an oxygen precursor gas pipeline to be in a closed state by an equipment controller, and controlling a mass flow controller MFC1 of the organic bismuth source gas carrier pipeline, a mass flow controller MFC2 of the organic aluminum source gas carrier pipeline, a mass flow controller MFC3 of the organic gallium source gas carrier pipeline and a mass flow controller MFC4 of the oxygen precursor gas carrier pipeline by the equipment controller, so that inert gas in each gas pipeline is introduced into the vacuum reaction cavity according to the set value in the step D);
pulse B is realized by the following actions:
controlling an automatic valve AK1 of the organic bismuth source pipeline to be in an open state, controlling an automatic valve AK2 of the organic aluminum source gas pipeline, an automatic valve AK3 of the organic gallium source gas pipeline and an automatic valve AK4 of the oxygen precursor gas pipeline to be in a closed state by the equipment controller, and controlling a mass flow controller MFC1 of the organic bismuth source gas-carrying pipeline, a mass flow controller MFC2 of the organic aluminum source gas-carrying pipeline, a mass flow controller MFC3 of the organic gallium source gas-carrying pipeline and a mass flow controller MFC4 of the oxygen precursor gas-carrying pipeline by the equipment controller so that gas in each gas pipeline is introduced into the vacuum reaction cavity according to the set value in the step D);
the pulse O is realized by the following actions:
controlling an automatic valve AK4 of an oxygen precursor gas pipeline to be in an open state, controlling an automatic valve AK1 of an organic bismuth source gas pipeline, an automatic valve AK2 of an organic aluminum source gas pipeline and an automatic valve AK3 of an organic gallium source gas pipeline to be in a closed state by a device controller, and controlling a mass flow controller MFC1 of the organic bismuth source gas carrier pipeline, a mass flow controller MFC2 of the organic aluminum source gas carrier pipeline, a mass flow controller MFC3 of the organic gallium source gas carrier pipeline and a mass flow controller MFC4 of the oxygen precursor gas carrier pipeline by the device controller, so that gas in each gas pipeline is introduced into the vacuum reaction cavity according to a set value in the step D);
the pulse G is realized by the following actions:
controlling an automatic valve AK3 of the organic gallium source gas pipeline to be in an open state, controlling an automatic valve AK1 of the organic bismuth source gas pipeline and an automatic valve AK3 of the oxygen precursor gas pipeline to be in a closed state by the equipment controller, and controlling a mass flow controller MFC1 of the organic bismuth source gas-carrying pipeline, a mass flow controller MFC2 of the organic aluminum source gas-carrying pipeline and a mass flow controller MFC3 of the oxygen precursor gas-carrying pipeline by the equipment controller so that gas in each gas pipeline is introduced into the vacuum reaction cavity according to the set value in the step D);
pulse a is achieved by the following actions:
controlling an automatic valve AK2 of the organic aluminum source gas pipeline to be in an open state, controlling an automatic valve AK1 of the organic bismuth source gas pipeline, an automatic valve AK3 of the organic gallium source gas pipeline and an automatic valve AK4 of the oxygen precursor gas pipeline to be in a closed state by the equipment controller, and controlling a mass flow controller MFC1 of the organic bismuth source gas-carrying pipeline, a mass flow controller MFC2 of the organic aluminum source gas-carrying pipeline, a mass flow controller MFC3 of the organic gallium source gas-carrying pipeline and a mass flow controller MFC4 of the oxygen precursor gas-carrying pipeline by the equipment controller, so that the gas in each gas pipeline is introduced into the vacuum reaction cavity according to the set value in the step;
the timing of these gas pulses is as follows:
there is one inert gas pulse before or after any one pulse of the organobismuth source gas or oxygen precursor gas or organoaluminum gas or organogallium gas, i.e., for example: BN … …, or GN … …, or ON … …, or AN … …, or … … NBN … …, or … … NGN … …, or … … NON … …, or … … NAN … …, where the ellipses "… …" represent other possible permutation sequences; and in the case where the above-mentioned condition is satisfied,
in the immediate vicinity of any one pulse of the organobismuth source gas, or of the organoaluminium gas, or of the organogallium gas, there is also a pulse of an oxygen precursor gas, i.e. for example: … … NONBN … …, or … … NONGN … …, or … … NBNON … …, or … … NONAN … …, or … … NGNON … …, where the ellipses "… …" represent other possible permutations; and in the case where the above-mentioned condition is satisfied,
the organic bismuth source gas pulse, the oxygen precursor gas pulse, the organic aluminum gas pulse, the organic gallium gas pulse and the inert gas pulse can be arranged in any order, and a plurality of organic bismuth source gas pulses or oxygen precursor gas pulses or organic aluminum gas pulses or organic gallium gas pulses and inert gas pulses are sequentially and continuously distributed and are next connected with one or more groups of other precursor gas pulses; in other words, the one or more pulses of the organo-aluminum gas, the one or more pulses of the organo-bismuth source gas, the one or more pulses of the organo-gallium source gas, and the one or more pulses of the introduced oxygen precursor gas may be arranged in any order, for example, the pulses of the organo-bismuth source gas, the pulses of the oxygen precursor gas, the pulses of the organo-aluminum source gas, the pulses of the organo-gallium source gas, and the pulses of the inert gas may be ordered as … … BNONBNONBNONBNONBNONGNONGNONGNONGNONBNONONGNONONONONBNONONONONONBNONONONONONNONNON … …, may be … … BNONBNONBNONBNONBNONBNONBNONONONONONONONONBNONBNONBNONONBNONONBNON … …, may be … … BNONGNONBNONBNONBNONONONONONBNONONBNONBNONON; the ellipses "… …" here represent other possible permutation sequences;
these gas pulse sequences are implemented by the apparatus controller controlling the opening and closing of the respective automatic valves, and programmed to perform a specific sequence of growth cycle cycles.
The number of individual gas pulses in one growth cycle is a multiple of 4 and not less than 12, for example: 12, 16, 20, 24 … …, etc.; each gas pulse is sequentially introduced into the vacuum reaction cavity through a pipeline, and the tray and the substrate are sequentially exposed in the gas atmosphere formed by the gas pulses; and the number of the first and second electrodes,
in one growth period, the sum of the number of the organic bismuth source gas pulses, the organic aluminum source gas pulses and the organic gallium source gas pulses is equal to the number of the oxygen precursor gas pulses, and the sum of the number of the organic bismuth source gas pulses, the organic gallium source gas pulses, the organic aluminum source gas pulses and the oxygen precursor gas pulses is equal to the number of the inert gas pulses;
in consideration of the steric effect of the organic precursor molecules, the number of the pulses of the organobismuth source gas and the pulses of the organoaluminum source gas and the organogallium source gas are not necessarily equal, but are distributed according to the following principle:
in a growth cycle, the stoichiometric ratio of bismuth, aluminum and gallium deposited on the substrate is close to 1:1, and a positive error of less than 10 percent is allowed, namely the stoichiometric ratio of bismuth and gallium is in a range of 1: 1-1: 1.1, which is due to the fact that proper compensation needs to be made by considering that bismuth is easy to volatilize in the step K of rapid thermal annealing;
in the case of satisfying the above requirements, the pulses of the organobismuth source gas and the pulses of the organoaluminum source gas are arranged so as to be uniformly distributed in time as much as possible in one growth cycle.
In order to facilitate the control of the growth cycle, generally speaking, the BNON pulse sequence, the GNON pulse sequence and the ANON pulse sequence are taken as the cyclic unit segments forming the growth cycle, the cyclic unit segments are arranged in any order in time, and according to the different types of the selected organic bismuth source, organic aluminum source gas and organic gallium source gas, one or more of the cyclic unit segments can also be independently cycled for multiple times and then arranged with other cyclic unit segments to form a growth cycle, for example: BNONGNONANON, or GNONANONBNON, or BNONBNONBNONBNONBNONBNONBNON, or BNONBNONBNONBNONBNONBNONGNON.
In order to obtain Bi (Al) with gradually changed components and crossing morphotropic phase boundaryxGa1-x)O3The film material is provided with two counters in each growth cycle controlled by a program, the two counters are used for setting and controlling the number of organic aluminum source gas pulses and organic gallium source gas pulses in each growth cycle respectively, and in the successive growth process, the value of one counter is gradually increased, and the value of the other counter is gradually decreased;
the growth equipment is controlled by a program, can be realized by a specially designed hardware circuit containing a counter, and can also be controlled by a singlechip or a PC through software; the counter refers to a digital counter circuit in a common meaning in a specially designed hardware circuit, and refers to two variables in a software program in a system formed by a single chip microcomputer or a PC mechanism.
In the process of preparing the film, the temperature of the vacuum reaction cavity, the flow rate and the pressure of the organic bismuth source, the organic aluminum source gas, the organic gallium source gas, the oxygen precursor and the inert gas are reasonably selected, so that the substrate material is exposed to the organic bismuth source and the organic bismuth source every timeWhen the organic aluminum source gas, the organic gallium source gas and the precursor gas are in the atmosphere, a monolayer of organic bismuth, organic aluminum or organic gallium can be completely adsorbed on the surface of the substrate material, and the adsorption mechanism is Langmuir adsorption; one film deposition is accomplished while the substrate is sequentially exposed to an atmosphere of two precursors, e.g., a layer of Bi is deposited while the substrate is subjected to a BNON pulse sequence2O3。
In the invention, the organic bismuth source gas pulse takes 2-8 s, the organic aluminum source gas pulse takes 0.1-2 s, the organic gallium source gas pulse takes 0.1-2 s, the oxygen precursor gas pulse takes 0.1-6 s, and basically, the chemical adsorption of each precursor molecule on the surface of the substrate is enough to complete one-time complete surface adsorption, and the coverage rate is close to 100%.
In any one precursor gas pulse, except the precursor molecules which are adsorbed on the surface of the substrate to form a molecular layer, the rest redundant precursor molecules are taken away by the inert gas pulse which follows the precursor molecules and are exhausted out of the vacuum reaction cavity by the vacuum pump, namely, after each half reaction on the surface of the substrate, at most one layer of certain precursor atoms is formed on the surface of the substrate.
In fact, generally speaking, due to the steric effect of the precursor molecules, or the shielding effect and the shadowing effect of the organic group, a layer of precursor atoms cannot be formed on the substrate surface after one "half-reaction", but a plurality of "half-reactions" are required to form a layer of precursor atoms on the substrate surface.
Based on the principle, the invention prepares Bi (Al)xGa1-x)O3The method of the film material can really realize the accurate control of the thickness when the film grows.
This is not comparable to any other thin film growth technique.
In the film preparation process, the substrate temperature is in the above-mentioned proper temperature window, and the chemisorption reaction on the substrate surface is all performed each time the substrate is exposed to the organic bismuth source gas atmosphere, the organic aluminum source gas atmosphere, the organic gallium source gas atmosphere and the oxygen precursor gas atmosphere "Half-reaction, rather than a complete chemisorption reaction, only two times of exposure of the substrate to the organic bismuth source gas atmosphere and the oxygen precursor gas atmosphere, or the organic aluminum source gas atmosphere and the oxygen precursor gas atmosphere, or the organic gallium source gas atmosphere and the oxygen precursor gas atmosphere, respectively, completes a complete chemisorption reaction, and respectively obtains Bi of one atomic layer2O3Or Ga2O3/Al2O3；
The method can realize the precise and controllable thickness during the film growth, but only obtains the material of at most one atomic layer in each growth, and has lower growth speed, so the method is generally used for growing Bi (Al) with the thickness of several nanometers to dozens of nanometersxGa1-x)O3Thin film materials, up to a few hundred nanometers, less than 500 nanometers, otherwise too low a growth rate may become unacceptable.
In the invention, the substrate can be Si or LaNiO3/Si、Pt/TiO2/SiO2/Si、Pt/Ti/SiO2/Si, but also other suitable substrates, e.g. TiN, SiO2And the like.
In the present invention, the term "inert gas" refers not only to inert gases (helium, argon, etc.) that are commonly referred to in the chemical art, but also includes other gases that do not chemically react with the precursor throughout the film preparation process, such as: nitrogen gas.
In the present invention, the oxygen precursor gas may be H2O、O2、O3Any one of the above gases, or a mixed gas of any two or three of them, wherein H is2O is deionized water, O2、O3The purity is higher than 99.999%.
In the invention, the organic bismuth source and the organic aluminum source gas are respectively tris (2,2,6, 6-tetramethyl-3, 5-heptanedionate) bismuth (III) and trimethylgallium;
under the condition that the equipment allows and meets the actual requirement, the organic bismuth source can also adopt triphenyl bismuth, trimethyl bismuth, tri-tert-butyl alcohol bismuth, trimethyl silyl bismuth and the like, and the organic aluminum source gas can also adopt triethyl gallium and tri-tert-butyl gallium.
Preferably, all gas pipelines connected to the vacuum reaction chamber are coated with heating belts, and the pipelines are heated by centralized power supply of the equipment controller so as to avoid condensation of various precursor gases in the pipelines;
preferably, the tray can be connected with a rotating shaft of a motor, the motor drives the tray to rotate at a constant speed in the film growth process, and the uniformity of the obtained film can be better by the substrate rotating mode.
Preferably, the device controller may be a customized dedicated circuit, may be formed by a PLC (programmable logic controller), may be formed by an FPGA (field programmable gate array), may be formed by a CPLD (complex programmable logic device), may be formed by a single chip microcomputer, or may be a PC.
The invention has the beneficial effects that:
preparation of Bi (Al) by Using the present inventionxGa1-x)O3The method of the film material can realize the Bi (Al) with gradually changed components and crossing the morphotropic phase boundaryxGa1-x)O3A thin film material, and Bi (Al)xGa1-x)O3The thickness of the film is precisely controllable, and Bi (Al)xGa1-x)O3The surface flatness of the film is greatly superior to that of the prior art.
Drawings
FIG. 1: preparation of Bi (Al)xGa1-x)O3A device for the thin-film material to be coated,
in fig. 1:1, an organic bismuth source container; k1, organic bismuth source pipeline manual valve; AK1, organic bismuth source pipeline automatic valve; MFC1, organic bismuth source carrier gas pipeline mass flow controller; 2, an organic aluminum source container; k2, organic aluminum source gas pipeline manual valve; AK2, organoaluminum source gas line automatic valve; MFC2, organoaluminum source gas carrier line mass flow controller; 3, an organic gallium source gas container; k3, manual valve of organic gallium source gas pipeline; AK3, organic gallium source gas pipeline automatic valve; MFC3, organic gallium source gas carrier pipeline mass flow controller; 4, an oxygen precursor gas source; k4, manual valve of oxygen precursor gas pipeline; AK4, oxygen precursor gas line automatic valve; MFC4, oxygen precursor gas carrier gas pipeline mass flow controller; 5, inert gas source; k5, manual valve of inert gas pipeline; AK5, automatic valve of vacuum pump air inlet;
the electric heaters of the semiconductor cooler, the vacuum gauge and the source container are not shown in fig. 1.
FIG. 2: n, B, O, A, G represents a nitrogen pulse, an organobismuth source gas pulse, an oxygen precursor gas pulse, an organoaluminum source gas pulse, and an organogallium source gas pulse, respectively.
FIG. 3: n, B, O, A, G represents a nitrogen pulse, an organobismuth source gas pulse, an oxygen precursor gas pulse, an organoaluminum source gas pulse, and an organogallium source gas pulse, respectively.
Detailed Description
The technical scheme of the invention is specifically described by combining the examples.
Example 1:
A) filling nitrogen with purity of more than 99.9995% into a vacuum glove box, and completing the following operations in the nitrogen atmosphere of the glove box: respectively filling an organic bismuth source, an organic aluminum source gas and an organic gallium source gas into an organic bismuth source container 1, an organic aluminum source gas container 2 and an organic gallium source container 3, and then installing and connecting the organic bismuth source, the organic aluminum source gas and the organic gallium source gas with respective pipelines;
B) the organic bismuth source adopts tris (2,2,6, 6-tetramethyl-3, 5-heptanedionato) bismuth (III), the organic gallium source gas adopts triethyl gallium, the organic aluminum source adopts triethyl aluminum, the oxygen precursor gas source adopts deionized water, and the inert gas adopts nitrogen with the purity of more than 99.9995%;
respectively filling an organic bismuth source, an organic aluminum source gas, an organic gallium source gas, an oxygen precursor gas source and nitrogen into an organic bismuth source container 1, an organic aluminum source gas container 2, an organic gallium source gas container 3, an oxygen precursor gas source container 4 and an inert gas source container 5, and then installing and connecting the organic bismuth source, the organic aluminum source gas, the organic gallium source gas, the oxygen precursor gas source container 4 and the inert gas source container 5 with respective pipelines;
and (3) expelling air in the pipeline after the raw material containers are installed and connected:
keeping the organic bismuth source pipeline manual valve K1, the organic aluminum source gas pipeline manual valve K2, the organic gallium source gas pipeline manual valve K3 and the oxygen precursor pipeline manual valve K4 in a closed state, then,
the automatic valve AK5 of the vacuum pump air inlet is controlled to be in an open state by the equipment controller, and the automatic valve AK1 of the organic bismuth source pipeline, the automatic valve AK2 of the organic aluminum source gas pipeline, the automatic valve AK3 of the organic gallium source gas pipeline and the automatic valve AK4 of the oxygen precursor gas pipeline are controlled to be in an open state by the equipment controller;
when a vacuum gauge in the vacuum reaction cavity is not changed any more, the automatic valve AK5 of the vacuum pump air inlet is controlled to be in a closed state by the equipment controller, and the quality flow controller MFC1 of the organic bismuth source gas-carrying pipeline, the quality flow controller MFC2 of the organic aluminum source gas-carrying pipeline, the quality flow controller MFC3 of the organic gallium source gas-carrying pipeline and the quality flow controller MFC4 of the oxygen precursor gas-carrying pipeline are controlled by the equipment controller, so that inert gas in each gas pipeline is introduced into the vacuum reaction cavity according to a certain value;
when the air pressure in the vacuum reaction cavity reaches 0.5 atmospheric pressure, the automatic valve AK5 of the air inlet of the vacuum pump is controlled to be in an open state by the equipment controller again, and the automatic valve AK1 of the organic bismuth source pipeline, the automatic valve AK2 of the organic aluminum source pipeline, the automatic valve AK3 of the organic gallium source gas pipeline and the automatic valve AK4 of the oxygen precursor gas pipeline are controlled to be in an open state by the equipment controller;
repeating the above process for 5 times;
C) blowing the cleaned TiN substrate material by inert gas, and placing the TiN substrate material into a substrate tray;
D) the tray and the TiN substrate are moved into a vacuum reaction cavity, a vacuum pump is started through an equipment controller, then an automatic valve AK5 of an air inlet of the vacuum pump is opened, and the vacuum reaction cavity is vacuumized;
E) setting the temperatures of the organic bismuth source container 1, the organic aluminum source gas container 2, the organic gallium source gas container 3 and the oxygen precursor gas source container 4 to 185 ℃, 20 ℃ and 20 ℃ on a device controller, and controlling the working states of an electric heater and/or a semiconductor refrigerator of the organic bismuth source container 1, the organic aluminum source container 2, the organic gallium source gas container 3 and the oxygen precursor gas source container 4 by the device controller so as to maintain the temperatures of the organic bismuth source container 1, the organic aluminum source gas container 2, the organic gallium source gas container 3 and the oxygen precursor gas source container 4 at set temperature values;
controlling an electric heater by an equipment controller to heat the vacuum cavity, so that the temperature of the tray and the substrate in the vacuum cavity is kept at 320 ℃ in the whole film growth process;
F) when the temperature of the vacuum cavity is constant at 320 ℃ for 30 minutes, setting the cycle number of film growth, the gas flow rate of an organic bismuth source gas-carrying pipeline, the gas flow rate of an organic aluminum source gas-carrying pipeline, the gas flow rate of an organic gallium source gas-carrying pipeline, the gas flow rate of an oxygen precursor gas-carrying pipeline, the flow rate of an inert gas, the pulse length of the organic bismuth source gas, the pulse length of the organic aluminum source gas, the pulse length of the organic gallium source gas, the pulse length of the oxygen precursor gas and the pulse length of the inert gas on an equipment controller; manually opening an organic bismuth source pipeline manual valve K1, an organic aluminum source gas pipeline manual valve K2, an organic gallium source gas pipeline manual valve K3, an oxygen precursor gas pipeline manual valve K4 and an inert gas pipeline manual valve K5;
setting the gas flow rate of an organic bismuth source gas carrier pipeline, the gas flow rate of an organic aluminum source gas carrier pipeline, the gas flow rate of an organic gallium source gas carrier pipeline and the gas flow rate of an oxygen precursor gas carrier pipeline to be 200sccm (standard cubicycentersmenters routine), 200sccm and 250sccm respectively on an input interface of an equipment controller;
setting the pulse length of tris (2,2,6, 6-tetramethyl-3, 5-heptanedionato) bismuth (III) gas to 5s, the pulse length of triethylaluminum to 0.4s, the pulse length of triethylgallium to 0.4s, and H on the input interface of the equipment controller2The pulse length of O gas is 0.1s, and the pulse length of nitrogen gas is 4 s;
b, A, G, O, N represent a bismuth (III) tris (2,2,6, 6-tetramethyl-3, 5-heptanedionate) gas pulse, a triethylaluminum gas pulse, a triethylgallium gas pulse, and H2O gas pulse and nitrogen gas pulse, wherein in the whole growth period, the gas pulse cycle sequence is shown in figure 2;
G) controlling an organic bismuth source gas-carrying pipeline mass flow controller MFC1, an organic aluminum source gas-carrying pipeline mass flow controller MFC2, an organic gallium source gas-carrying pipeline mass flow controller MFC3 and an oxygen precursor gas-carrying pipeline mass flow controller MFC4 by an equipment controller, so that the gas in each gas pipeline is introduced into a vacuum reaction cavity according to the set value in the step F), and the inert gas, the organic bismuth source gas, the organic gallium source gas, the oxygen precursor gas and the organic aluminum source gas are respectively introduced into the vacuum reaction cavity according to a certain gas pulse time sequence; all precursor gases are respectively transported by adopting nitrogen;
the gas pulse sequence is composed of an inert gas pulse, an organic bismuth source gas pulse, an organic gallium source gas pulse, an oxygen precursor gas pulse and an organic aluminum source gas pulse, and if N, B, O, A, G represents the inert gas pulse, the organic bismuth source gas pulse, the oxygen precursor gas pulse, the organic aluminum source gas pulse and the organic gallium source gas pulse, respectively, then:
the pulse N is realized by the following actions:
controlling an automatic valve AK1 of an organic bismuth source pipeline, an automatic valve AK2 of an organic aluminum source gas pipeline, an automatic valve AK3 of an organic gallium source gas pipeline and an automatic valve AK4 of an oxygen precursor gas pipeline to be in a closed state by an equipment controller, and controlling a mass flow controller MFC1 of the organic bismuth source gas carrier pipeline, a mass flow controller MFC2 of the organic aluminum source gas carrier pipeline, a mass flow controller MFC3 of the organic gallium source gas carrier pipeline and a mass flow controller MFC4 of the oxygen precursor gas carrier pipeline by the equipment controller, so that inert gas in each gas pipeline is introduced into the vacuum reaction cavity according to the set value in the step D);
pulse B is realized by the following actions:
controlling an automatic valve AK1 of the organic bismuth source pipeline to be in an open state, controlling an automatic valve AK2 of the organic aluminum source gas pipeline, an automatic valve AK3 of the organic gallium source gas pipeline and an automatic valve AK4 of the oxygen precursor gas pipeline to be in a closed state by the equipment controller, and controlling a mass flow controller MFC1 of the organic bismuth source gas-carrying pipeline, a mass flow controller MFC2 of the organic aluminum source gas-carrying pipeline, a mass flow controller MFC3 of the organic gallium source gas-carrying pipeline and a mass flow controller MFC4 of the oxygen precursor gas-carrying pipeline by the equipment controller so that gas in each gas pipeline is introduced into the vacuum reaction cavity according to the set value in the step D);
the pulse O is realized by the following actions:
controlling an automatic valve AK4 of an oxygen precursor gas pipeline to be in an open state, controlling an automatic valve AK1 of an organic bismuth source gas pipeline, an automatic valve AK2 of an organic aluminum source gas pipeline and an automatic valve AK3 of an organic gallium source gas pipeline to be in a closed state by a device controller, and controlling a mass flow controller MFC1 of the organic bismuth source gas carrier pipeline, a mass flow controller MFC2 of the organic aluminum source gas carrier pipeline, a mass flow controller MFC3 of the organic gallium source gas carrier pipeline and a mass flow controller MFC4 of the oxygen precursor gas carrier pipeline by the device controller, so that gas in each gas pipeline is introduced into the vacuum reaction cavity according to a set value in the step D);
the pulse G is realized by the following actions:
controlling an automatic valve AK3 of the organic gallium source gas pipeline to be in an open state, controlling an automatic valve AK1 of the organic bismuth source gas pipeline and an automatic valve AK3 of the oxygen precursor gas pipeline to be in a closed state by the equipment controller, and controlling a mass flow controller MFC1 of the organic bismuth source gas-carrying pipeline, a mass flow controller MFC2 of the organic aluminum source gas-carrying pipeline and a mass flow controller MFC3 of the oxygen precursor gas-carrying pipeline by the equipment controller so that gas in each gas pipeline is introduced into the vacuum reaction cavity according to the set value in the step D);
pulse a is achieved by the following actions:
controlling an automatic valve AK2 of the organic aluminum source gas pipeline to be in an open state, controlling an automatic valve AK1 of the organic bismuth source gas pipeline, an automatic valve AK3 of the organic gallium source gas pipeline and an automatic valve AK4 of the oxygen precursor gas pipeline to be in a closed state by the equipment controller, and controlling a mass flow controller MFC1 of the organic bismuth source gas-carrying pipeline, a mass flow controller MFC2 of the organic aluminum source gas-carrying pipeline, a mass flow controller MFC3 of the organic gallium source gas-carrying pipeline and a mass flow controller MFC4 of the oxygen precursor gas-carrying pipeline by the equipment controller, so that the gas in each gas pipeline is introduced into the vacuum reaction cavity according to the set value in the step;
H) when the film growth cycle times reach the set times, the film thickness reaches the required value, a BAG film material with a certain thickness is obtained, the device controller closes the automatic valve AK1 of the organic bismuth source pipeline, the automatic valve AK2 of the organic aluminum source gas pipeline, the automatic valve AK3 of the organic gallium source pipeline and the automatic valve AK3 of the oxygen precursor gas pipeline, the organic bismuth source, the organic aluminum source gas, the organic gallium source gas and the oxygen precursor gas are stopped to be introduced, the inert gas is continuously introduced, the power supply of the electric heater is stopped, and the heating of the vacuum cavity is stopped;
I) manually closing an organic bismuth source pipeline manual valve K1, an organic aluminum source gas pipeline manual valve K2, an organic gallium source gas pipeline manual valve K3, an oxygen precursor gas pipeline manual valve K4, an inert gas pipeline manual valve K5 and a vacuum pump air inlet automatic valve AK4 to keep an open state, and naturally cooling a vacuum reaction cavity;
J) when the vacuum cavity reaches or approaches to the room temperature, the automatic valve AK5 of the vacuum pump air inlet is closed by the equipment controller;
K) inflating the vacuum reaction cavity to make the air pressure of the vacuum reaction cavity reach one atmospheric pressure, and the air pressure inside and outside the vacuum reaction cavity reach a balanced state;
l) taking out the substrate deposited with the BAG film material, and closing the manual valve K5 of the inert gas pipeline;
m) putting the substrate attached with the BAG film material obtained in the step L into a rapid annealing furnace, performing rapid thermal annealing treatment, naturally cooling, taking out, and testing to verify that the space group of the obtained BAG film material is Pcca;
the rapid thermal annealing comprises the following steps:
(a) maintaining at 220 deg.C for 3 min;
(b) maintaining at 360 deg.C for 4 min;
(c) annealing at 950 deg.C for 4 min;
and (5) carrying out performance test on the sample.
Example 2:
the basic procedure is as in example 1.
The differences are as follows:
the organic bismuth source adopts triethyl bismuth, the organic gallium source gas adopts triethyl gallium, the organic aluminum source gas adopts triethyl aluminum, the oxygen precursor gas source adopts deionized water, and the inert gas adopts nitrogen with the purity of more than 99.9995 percent;
setting the temperatures of an organic bismuth source container 1, an organic aluminum source gas container 2, an organic gallium source gas container 3 and an oxygen precursor gas source container 4 to be 25 ℃, 20 ℃ and 20 ℃ respectively on an equipment controller;
setting the gas flow rate of an organic bismuth source gas carrier pipeline, the gas flow rate of an organic aluminum source gas carrier pipeline, the gas flow rate of an organic gallium source gas carrier pipeline and the gas flow rate of an oxygen precursor gas carrier pipeline to be 200sccm (standard cubicycentersmenters routine), 200sccm and 200sccm respectively on an input interface of an equipment controller;
setting the pulse length of triethyl bismuth gas to be 0.5s, the pulse length of triethyl aluminum gas to be 0.4s, the pulse length of triethyl gallium gas to be 0.4s and H on the input interface of the device controller2The pulse length of O gas is 0.1s, and the pulse length of nitrogen gas is 4 s;
b, A, G, O, N respectively represent triethyl bismuth gas pulse, triethyl aluminum gas pulse, triethyl gallium gas pulse, H2O gas pulse and nitrogen gas pulse, wherein in the whole growth period, the gas pulse cycle sequence is shown in figure 3;
and D, putting the substrate attached with the BAG film material obtained in the step L into a rapid annealing furnace, performing rapid thermal annealing treatment, naturally cooling and taking out.

Claims (13)

1. Bi (Al) with gradually changed componentsxGa1-x)O3An apparatus for atomic layer deposition of a thin film material, the apparatus comprising: the device comprises a vacuum reaction cavity, a vacuum pump, an oxygen precursor gas source container, an inert gas container and a device controller;
the method is characterized in that:
the device still includes: two counters, an organic bismuth source container, an organic bismuth source pipeline manual valve, an organic bismuth source pipeline automatic valve, an organic bismuth source gas-carrying pipeline mass flow controller, an organic aluminum source gas container, an organic aluminum source gas pipeline manual valve, an organic aluminum source gas pipeline automatic valve, an organic aluminum source gas-carrying pipeline mass flow controller, an organic gallium source container, an organic gallium source gas pipeline manual valve, an organic gallium source gas pipeline automatic valve, an organic gallium source gas-carrying pipeline mass flow controller, an oxygen precursor gas pipeline manual valve, an oxygen precursor gas pipeline automatic valve, an oxygen precursor gas-carrying pipeline mass flow controller, an inert gas pipeline manual valve and a vacuum pump gas inlet automatic valve;
sequentially introducing an organic bismuth source gas pulse, an organic aluminum source gas pulse, an organic gallium source gas pulse, an oxygen precursor gas pulse and an inert gas pulse into the vacuum reaction cavity according to a certain sequence;
the two counters are respectively used for setting and controlling the number of the organic aluminum source gas pulses and the organic gallium source gas pulses in each growth period, and in the successive growth process, the value of one counter is gradually increased, and the value of the other counter is gradually decreased; the equipment controller is composed of a PLC, an FPGA, a CPLD, a singlechip system, a computer or a specially designed circuit system;
when the counter is realized by adopting a hardware circuit, the counter is a digital counter circuit; when the counter is implemented by adopting a program, the counter is a variable in a software program;
the gas pulse sequence is realized by controlling the opening and closing of automatic valves in each gas pipeline by a device controller, and the growth cycle of the gas pulse sequence is executed.
2. A device as claimed in claim 1, wherein:
the outlet of the organic bismuth source container is sequentially connected with the manual valve of the organic bismuth source pipeline, the automatic valve of the organic bismuth source pipeline and the vacuum reaction cavity through a gas pipeline, the outlet of the organic aluminum source gas container is sequentially connected with the manual valve of the organic aluminum source gas pipeline, the automatic valve of the organic aluminum source gas pipeline and the vacuum reaction cavity through a gas pipeline, the outlet of the organic gallium source gas container is sequentially connected with the manual valve of the organic gallium source gas pipeline, the automatic valve of the organic gallium source gas pipeline and the vacuum reaction cavity through a gas pipeline, the outlet of the oxygen precursor gas source container is sequentially connected with the manual valve of the oxygen precursor gas pipeline, the automatic valve of the oxygen precursor gas pipeline and the vacuum reaction cavity through a gas pipeline, the outlet of the inert gas container is connected with the manual valve of the inert gas pipeline through a gas pipeline and is respectively connected with the mass, The mass flow controller of the organic aluminum source gas carrier pipeline, the mass flow controller of the organic gallium source gas carrier pipeline and the mass flow controller of the oxygen precursor gas carrier pipeline are connected, the outlet of the mass flow controller of the organic bismuth source gas carrier pipeline is connected on a gas pipeline between the automatic valve of the organic bismuth source pipeline and the vacuum reaction cavity through a three-way connecting piece, the outlet of the mass flow controller of the organic aluminum source gas carrier pipeline is connected on a gas pipeline between the automatic valve of the organic aluminum source gas pipeline and the vacuum reaction cavity through a three-way connecting piece, the outlet of the mass flow controller of the organic gallium source gas carrier pipeline is connected on a gas pipeline between the automatic valve of the organic aluminum pipeline and the vacuum reaction cavity through a three-way connecting piece, the outlet of the mass flow controller of the oxygen precursor gas carrier pipeline is connected on a gas pipeline between the automatic valve of the organic bismuth source pipeline and the vacuum reaction cavity, the outlet of the vacuum reaction cavity is sequentially connected to the automatic valve of the vacuum pump air inlet and the air inlet of the vacuum pump through pipelines.
3. A device as claimed in claim 1, wherein:
at any moment, the device controller controls at most one of the automatic valve of the organic bismuth source pipeline, the automatic valve of the organic aluminum source gas pipeline, the automatic valve of the organic gallium source gas pipeline and the automatic valve of the oxygen precursor gas pipeline to be in an open state, and the rest of the valves are in a closed state; or the automatic valve of the organic bismuth source pipeline, the automatic valve of the organic aluminum source gas pipeline, the automatic valve of the organic gallium source gas pipeline and the automatic valve of the oxygen precursor gas pipeline are all in a closed state.
4. A device as claimed in claim 1, wherein:
the organic bismuth source pipeline manual valve, the organic aluminum source gas pipeline manual valve, the organic gallium source gas pipeline manual valve, the oxygen precursor gas pipeline manual valve and the inert gas pipeline manual valve are all manually opened by operators and are controlled by an uncontrolled controller.
5. A device as claimed in claim 1, wherein:
the device comprises a vacuum gauge, an automatic valve of an organic bismuth source pipeline, a mass flow controller of an organic bismuth source gas carrying pipeline, an automatic valve of an organic aluminum source gas pipeline, a mass flow controller of an organic aluminum source gas carrying pipeline, an automatic valve of an organic gallium source gas pipeline, a mass flow controller of an organic gallium source gas carrying pipeline, an oxygen precursor gas source container, an automatic valve of an oxygen precursor gas pipeline, a mass flow controller of an oxygen precursor gas carrying pipeline, a vacuum reaction cavity, a vacuum pump, an automatic valve of a vacuum pump gas inlet, an electric heater in the vacuum reaction cavity, a temperature sensor, an organic bismuth source container, an organic aluminum source gas container, an organic gallium source gas container, an electric heater of the oxygen precursor gas source container and a semiconductor refrigerator, which are all connected to a device controller through cables, and the device controller is used for.
6. A device as claimed in claim 1, wherein:
a vacuum gauge is arranged in the vacuum cavity.
7. A device as claimed in claim 1, wherein:
the collected data of the temperature sensor is transmitted to the equipment controller through a cable so as to realize proportional-integral-differential control of the temperature.
8. A device as claimed in claim 1, wherein:
an electric heater and a temperature sensor are arranged in the vacuum reaction cavity, and the organic bismuth source container, the organic aluminum source gas container and the oxygen precursor gas source container are respectively provided with the electric heater and a semiconductor refrigerator.
9. A device as claimed in claim 1, wherein:
the working states of the electric heater and the semiconductor refrigerator of the organic bismuth source container, the organic aluminum source gas container, the organic gallium source gas container and the oxygen precursor gas source container are controlled by the equipment controller, so that the temperatures of the organic bismuth source container, the organic aluminum source gas container, the organic gallium source gas container and the oxygen precursor gas source container are kept at the set temperature values.
10. A device as claimed in claim 1, wherein:
the tray is driven by a motor to drive the substrate to rotate at a constant speed.
11. A device as claimed in claim 1, wherein:
all gas lines connected to the vacuum reaction chamber are covered with heating tape.
12. An apparatus as claimed in claim 11, wherein:
all gas pipelines are heated by centralized power supply of the equipment controller.
13. A device as claimed in claim 1, wherein:
n, B, O, A, G respectively represent the inert gas pulse, the organic bismuth source gas pulse, the oxygen precursor gas pulse, the organic aluminum source gas pulse and the organic gallium source gas pulse, then:
the pulse N is realized by the following actions:
the device controller controls an automatic valve of an organic bismuth source pipeline, an automatic valve of an organic aluminum source gas pipeline, an automatic valve of an organic gallium source gas pipeline and an automatic valve of an oxygen precursor gas pipeline to be in a closed state, and controls a mass flow controller of an organic bismuth source gas carrier pipeline, a mass flow controller of an organic aluminum source gas carrier pipeline, a mass flow controller of an organic gallium source gas carrier pipeline and a mass flow controller of an oxygen precursor gas carrier pipeline, so that inert gas in each gas pipeline is introduced into the vacuum reaction cavity according to a set value;
pulse B is realized by the following actions:
the device controller controls the organic bismuth source pipeline automatic valve to be in an open state, the organic aluminum source gas pipeline automatic valve, the organic gallium source gas pipeline automatic valve and the oxygen precursor gas pipeline automatic valve to be in a closed state, and the device controller controls the organic bismuth source gas carrying pipeline mass flow controller, the organic aluminum source gas carrying pipeline mass flow controller, the organic gallium source gas carrying pipeline mass flow controller and the oxygen precursor gas carrying pipeline mass flow controller, so that gas in each gas pipeline is introduced into the vacuum reaction cavity according to a set value;
the pulse O is realized by the following actions:
the device controller controls the automatic valve of the oxygen precursor gas pipeline to be in an open state, the automatic valve of the organic bismuth source pipeline, the automatic valve of the organic aluminum source gas pipeline and the automatic valve of the organic gallium source gas pipeline to be in a closed state, and the device controller controls the mass flow controller of the organic bismuth source gas carrier pipeline, the mass flow controller of the organic aluminum source gas carrier pipeline, the mass flow controller of the organic gallium source gas carrier pipeline and the mass flow controller of the oxygen precursor gas carrier pipeline, so that gas in each gas pipeline is introduced into the vacuum reaction cavity according to a set value;
the pulse G is realized by the following actions:
the device controller controls the automatic valve of the organic gallium source gas pipeline to be in an open state, the automatic valve of the organic bismuth source gas pipeline and the automatic valve of the oxygen precursor gas pipeline to be in a closed state, and the device controller controls the mass flow controller of the organic bismuth source gas-carrying pipeline, the mass flow controller of the organic aluminum source gas-carrying pipeline and the mass flow controller of the oxygen precursor gas-carrying pipeline, so that gas in each gas pipeline is introduced into the vacuum reaction cavity according to a set value;
pulse a is achieved by the following actions:
the device controller controls the automatic valve of the organic aluminum source gas pipeline to be in an open state, the automatic valve of the organic bismuth source gas pipeline, the automatic valve of the organic gallium source gas pipeline and the automatic valve of the oxygen precursor gas pipeline to be in a closed state, and controls the mass flow controller of the organic bismuth source gas carrier pipeline, the mass flow controller of the organic aluminum source gas carrier pipeline, the mass flow controller of the organic gallium source gas carrier pipeline and the mass flow controller of the oxygen precursor gas carrier pipeline, so that the gas in each gas pipeline is introduced into the vacuum reaction cavity according to the set values in the steps.
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