WO2014089864A1 - Method for preparing co-doped zinc oxide thin film through atomic layer deposition - Google Patents

Method for preparing co-doped zinc oxide thin film through atomic layer deposition Download PDF

Info

Publication number
WO2014089864A1
WO2014089864A1 PCT/CN2012/086981 CN2012086981W WO2014089864A1 WO 2014089864 A1 WO2014089864 A1 WO 2014089864A1 CN 2012086981 W CN2012086981 W CN 2012086981W WO 2014089864 A1 WO2014089864 A1 WO 2014089864A1
Authority
WO
WIPO (PCT)
Prior art keywords
deposition
source
doping
preparation
donor
Prior art date
Application number
PCT/CN2012/086981
Other languages
French (fr)
Chinese (zh)
Inventor
卢维尔
夏洋
李超波
解婧
李楠
Original Assignee
中国科学院微电子研究所
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 中国科学院微电子研究所 filed Critical 中国科学院微电子研究所
Publication of WO2014089864A1 publication Critical patent/WO2014089864A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/407—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
    • C23C16/45536—Use of plasma, radiation or electromagnetic fields

Definitions

  • the invention relates to the technical field of preparation of oxidized films, and in particular to a method for preparing a co-doped oxidized film by atomic layer deposition.
  • Semiconductor thin films play an important role in high-tech industries such as microelectronics, optics, and information science. They develop high-crystal quality semiconductor thin film preparation and doping technology, especially for the preparation and characterization of third-generation semiconductor materials ZnO thin films. The study of doping characteristics is of great significance for important applications such as ultraviolet luminescent materials, ultraviolet detectors, highly integrated photonics and electronics devices, and solar cells for new energy sources. Oxidation as a new type II-VI direct band gap wide bandgap compound, with a large room temperature band gap of 3.37 eV, and free exciton binding energy of up to 60 meV, as a semiconductor material has received more and more attention.
  • ZnO thin films Compared with other wide-bandgap semiconductor materials, ZnO thin films have low growth temperature, good radiation resistance, low threshold power and high energy conversion efficiency. These advantages make ZnO become optoelectronics, microelectronics, and information. The key basic materials that high-tech will continue to develop after the 12th Five-Year Plan. However, due to the defects of intrinsic ZnO, ZnO is n-type, and the preparation of p-type ZnO thin films is a hot and difficult point in ZnO research.
  • the acceptor-donor-acceptor co-doping is considered to be one of the directions for the optimal development of high-quality p-ZnO thin films.
  • methods for preparing ZnO thin films generally include: magnetron sputtering, metal organic chemical vapor deposition (MOCVD), molecular beam epitaxy (MBE), laser pulse deposition (PLD), and wet chemical deposition.
  • MOCVD metal organic chemical vapor deposition
  • MBE molecular beam epitaxy
  • PLD laser pulse deposition
  • wet chemical deposition these preparation processes have their own advantages and disadvantages, from the crystallization point of view by MOCVD and MBE
  • MOCVD cannot do film doping in situ and the turbulence and gas flow distribution present in the reaction can affect the thickness and uniformity of the film.
  • the precise doping of MBE technology for specific atomic layer locations is also difficult to achieve.
  • the technical problem to be solved by the present invention is to provide an in-situ donor-acceptor co-doping of an oxidized film to increase the amount of acceptor elements and promote atomic layer deposition of p-type transition of the oxidized film.
  • the present invention provides a method for preparing a co-doped oxidized film by atomic layer deposition, comprising:
  • the substrate is placed in an ALD reaction chamber, and the substrate and the chamber tube are heated, and then multi-component composite deposition is sequentially performed;
  • the composite deposition includes doping deposition of a donor dopant source containing 111 main group elements X, second derivation deposition, at least two nitrogen dopant source depositions, and at least two times after deposition of the first source.
  • the deposition sequence with the second source is a second source deposition, followed by a donor dopant source deposition of the ruthenium main group element.
  • the method for preparing a co-doped oxidized film by atomic layer deposition adopts an atomic layer deposition method to utilize the characteristics of atomic layer deposition layer growth, and incorporates two acceptor elements N during the growth process of the oxidized film. And a primary host donor doping element X (X may be B, Al, In, Ga) to form an acceptor-donor-acceptor co-doped oxidized film.
  • X may be B, Al, In, Ga
  • the co-doping of the donor and the acceptor can reduce the Madron energy of the system, increase the amount of the acceptor element, and facilitate the ⁇ -type transformation of the oxidized film.
  • the preparation process of the invention is simple, and the deposition and doping process is easy to control.
  • the prepared co-doped oxidized film is beneficial to improve the stability of the p-type electrical properties of the oxidized film.
  • FIG. 1 is a method for preparing a co-doped oxidized film by atomic layer deposition according to an embodiment of the present invention
  • the present invention provides a method for preparing a co-doped oxidized film by atomic layer deposition, comprising:
  • the substrate is pre-processed and placed in an ALD chamber;
  • the ALD chamber was purged with high purity nitrogen. The method of the film is explained.
  • concentrated acid: hydrogen peroxide 4:1.
  • the flow rate of nitrogen gas is from 1 sccm to 1000 sccm, preferably 15 sccm
  • the intake time is from 0.04 s to 5 s, preferably 0.15 s
  • the cleaning time is from 5 s to 150 s, preferably 50 s
  • the substrate temperature It is from 100 ° C to 500 ° C, preferably 300 ° C
  • the plasma discharge power is from 1 W to 100 W, preferably 50 W
  • the discharge time is from 1 s to 50 s, preferably 10 s.
  • N doping is introduced by N 2 plasma
  • B atom is supplied by BF 3
  • deposition of two plasma N 2 and primary BF 3 is performed, so that B is substituted in ZnO ( ⁇ ⁇ ⁇ ), and N is substituted for O.
  • Forming a complex of N-Zr-N in the film which can reduce the ionization energy and promote the formation of p-type conductance.
  • the NBN co-doped oxidized film can be grown layer by layer.
  • concentrated acid: hydrogen peroxide 4:1.
  • the flow rate of nitrogen is from 1 sccm to 1000 sccm, preferably 15 sccm
  • the intake time is 0.04 s to 5 s, preferably 0.15 s
  • the cleaning time is from 5 s to 150 s, preferably 50 s
  • the substrate temperature is It is from 100 ° C to 500 ° C, preferably 300 ° C
  • the plasma discharge power is from 1 W to 100 W, preferably 50 W
  • the discharge time is from 1 s to 50 s, preferably 10 s.
  • N 2 plasma doping N by A1 (CH 3) 3 to provide A1 atoms
  • a N 2 twice Plasma A1 (CH 3) 3 is deposited, so that for speech in ZnO A1 ( Alz recommendation), N replaces the position of 0, forms a co-doping of N-A1-N in the oxidized film, repeats the composite deposition of the multi-component, and can grow the N-A1-N co-doped oxidized film layer by layer. Promote p-type conductance Formed.
  • the flow rate of nitrogen gas is from 1 sccm to 1000 sccm, preferably 15 sccm
  • the intake time is from 0.04 s to 5 s, preferably 0.15 s
  • the cleaning time is from 5 s to 150 s, preferably 50 s
  • the substrate temperature is It is from 100 ° C to 500 ° C, preferably 300 ° C
  • the plasma discharge power is from 1 W to 100 W, preferably 50 W
  • the discharge time is from 1 s to 50 s, preferably 10 s.
  • N doping is introduced by N 2 plasma, In (CH 2 CH 3 ) 3 is supplied to provide In atoms, and two plasma N 2 and one In (CH 2 CH 3 ) 3 are deposited, so that In is in ZnO.
  • Neutral (In Zn ) N replaces the position of 0, forms N-In-N co-doping in the film, repeats the multi-component composite deposition, and can grow the N-In-N co-doped oxidized film layer by layer.
  • Co-doping is beneficial to increase the doping amount of the acceptor element and promote the formation of p-type conductance.
  • concentrated acid: hydrogen peroxide 4:1.
  • the flow rate of nitrogen is from 1 sccm to 1000 sccm, preferably 15 sccm
  • the intake time is from 0.04 s to 5 s, preferably 0.15 s
  • the cleaning time is from 5 s to 1500 s, preferably 50 s.
  • the temperature is from 100 ° C to 500 ° C, preferably 300 ° C ; wherein the plasma discharge power is 1 W - 100 W, preferably 50 W, and the discharge time is 1 s - 50 s, preferably 10 s.
  • Ga(CH 2 CH 3 ) 3 is used to provide Ga atoms, two depositions of plasma N 2 and one time of Ga(CH 2 CH 3 ) 3 , such that Ga replaces (Ga Zn ) in ZnO, and N replaces the position of 0.
  • the co-doping of N-Ga-N is formed in the film, and the multi-component composite deposition is repeated, and the N-Ga-N co-doped oxidized film can be grown layer by layer. Co-doping is beneficial to increase the doping amount of the acceptor element and promote the formation of p-type conductance.
  • the film during which N atoms are generated by N 2 plasma, the donor dopant atoms are provided by the III main group gas source, and the deposition of the two plasma N 2 and the primary donor doping source causes the bismuth main donor to be doped
  • the heteroelement X (X can be B, Al, In, Ga) in ZnO (X Zn ), N replaces the position of O, forms co-doping of NXN in the film, co-doping can reduce the ionization energy, It is beneficial to increase the doping amount of the acceptor element and promote the formation of p-type conductance.
  • the NXN co-doped oxidized film can be grown layer by layer.
  • the method provided by the invention can realize the co-doping of the doping element X (X can be B, Al, In, Ga) with the N element of the main group of the ruthenium, and the method is simple, and the characteristics of the single layer circulation growth by atomic layer deposition are adopted.
  • X can be B, Al, In, Ga
  • donor-acceptor co-doping oxidized film can reduce the system's hungry madron energy, increase the doping concentration of N, and also get more The shallow acceptor level is conducive to the formation of p-type conductance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Plasma & Fusion (AREA)
  • Electromagnetism (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

Disclosed is a method for preparing a co-doped zinc oxide thin film through atomic layer deposition, which comprises: placing a substrate in an ALD reaction chamber, heating the substrate and a chamber pipeline, and performing multi-component composite deposition, wherein the composite deposition comprises: after primary zinc source deposition, respectively introducing doping deposition of a donor doping source containing a III main group element X for one time, secondary zinc source deposition, nitrogen-doping source deposition for at least two times, and oxygen source deposition for at least two times, to form N-X-N co-doping; the sequence of the nitrogen-doping source deposition and the oxygen source deposition is that the nitrogen-doping source deposition is performed before the oxygen source deposition; and the sequence of the deposition of the donor doping source containing the III main group element and the secondary zinc source deposition is that the secondary zinc source deposition is performed before the deposition of the donor doping source containing the III main group element. The method can perform in-situ donor-acceptor co-doping on the zinc oxide thin film, to increase the doped amount of the acceptor element, and facilitate p-type conversion of the zinc oxide thin film.

Description

原子层沉积制备共掺的氧化锌薄膜的方法 技术领域  Method for preparing co-doped zinc oxide thin film by atomic layer deposition
本发明涉及氧化辞薄膜的制备技术领域， 特别涉及原子层沉积制备共 掺的氧化辞薄膜的方法。  The invention relates to the technical field of preparation of oxidized films, and in particular to a method for preparing a co-doped oxidized film by atomic layer deposition.
背景技术 Background technique
半导体薄膜在微电子、 光学、 信息学等高新技术产业中发挥出十分重 要的作用， 发展高晶体质量半导体薄膜的制备与掺杂技术， 特别是对于第 三代半导体材料 ZnO薄膜的制备、 表征、 掺杂极其特性研究， 对于包括紫 外波段发光材料、 紫外探测器， 高集成度光子学与电子学器件、 太阳能电 池等面向新能源的重要应用领域具有十分重要的意义。 氧化辞作为一种新 型的 II - VI族直接带隙宽禁带化合物， 具有大的室温禁带宽度 3.37eV, 而 且自由激子结合能高达 60meV, 作为半导体材料越来越受到人们的重视。 与其它宽禁带半导体材料相比， ZnO薄膜生长温度低， 抗辐射性好， 受激 辐射有较低的阈值功率和很高的能量转换效率，这些优点使 ZnO正成为光 电子、 微电子、 信息等高新技术在十二五之后赖以继续发展的关键基础材 料。 然而本征 ZnO由于存在缺陷， 使得 ZnO呈 n型， p型 ZnO薄膜制备 是目前 ZnO相关研究的热点和难点。氮掺杂虽然在理论上的计算使得 p型 ZnO的制备成为可能， 但是众多实验表明， 由于 N元素在 ZnO中固溶度 较低， 因此单独的 N元素掺杂不能实现高载流子浓度和高迁移率的 p型 ZnO薄膜。 为了解决该问题， 受主 -施主 -受主的共掺被认为是制备出高质 量的 p-ZnO薄膜最优发展前景的方向之一。  Semiconductor thin films play an important role in high-tech industries such as microelectronics, optics, and information science. They develop high-crystal quality semiconductor thin film preparation and doping technology, especially for the preparation and characterization of third-generation semiconductor materials ZnO thin films. The study of doping characteristics is of great significance for important applications such as ultraviolet luminescent materials, ultraviolet detectors, highly integrated photonics and electronics devices, and solar cells for new energy sources. Oxidation as a new type II-VI direct band gap wide bandgap compound, with a large room temperature band gap of 3.37 eV, and free exciton binding energy of up to 60 meV, as a semiconductor material has received more and more attention. Compared with other wide-bandgap semiconductor materials, ZnO thin films have low growth temperature, good radiation resistance, low threshold power and high energy conversion efficiency. These advantages make ZnO become optoelectronics, microelectronics, and information. The key basic materials that high-tech will continue to develop after the 12th Five-Year Plan. However, due to the defects of intrinsic ZnO, ZnO is n-type, and the preparation of p-type ZnO thin films is a hot and difficult point in ZnO research. Although the theoretical calculation of nitrogen doping makes the preparation of p-type ZnO possible, many experiments have shown that due to the low solid solubility of N element in ZnO, the single N element doping cannot achieve high carrier concentration and High mobility p-type ZnO thin film. In order to solve this problem, the acceptor-donor-acceptor co-doping is considered to be one of the directions for the optimal development of high-quality p-ZnO thin films.
近年来， 制备 ZnO薄膜的方法通常包括： 如磁控溅射、 金属有机化学 气相沉积 (MOCVD)、 分子束外延 (MBE)、 激光脉沖沉积 (PLD)和湿化学沉 积等。 这些制备工艺各有优缺点， 从结晶情况来看以 MOCVD和 MBE法 制备的薄膜质量较好。 然而， MOCVD不能在原位进行薄膜的掺杂并且反 应中存在的湍流和气流分布会影响膜的厚度和均勾性。 MBE技术对于特定 原子层位置的精确掺杂也难以实现。 In recent years, methods for preparing ZnO thin films generally include: magnetron sputtering, metal organic chemical vapor deposition (MOCVD), molecular beam epitaxy (MBE), laser pulse deposition (PLD), and wet chemical deposition. These preparation processes have their own advantages and disadvantages, from the crystallization point of view by MOCVD and MBE The prepared film is of good quality. However, MOCVD cannot do film doping in situ and the turbulence and gas flow distribution present in the reaction can affect the thickness and uniformity of the film. The precise doping of MBE technology for specific atomic layer locations is also difficult to achieve.
发明内容 Summary of the invention
本发明所要解决的技术问题是提供一种可以对氧化辞薄膜进行原位的 施主-受主的共掺， 以增加受主元素的掺入量， 促进氧化辞薄膜的 p型转变 的原子层沉积制备共掺的氧化辞薄膜的方法。  The technical problem to be solved by the present invention is to provide an in-situ donor-acceptor co-doping of an oxidized film to increase the amount of acceptor elements and promote atomic layer deposition of p-type transition of the oxidized film. A method of preparing a co-doped oxidized film.
为解决上述技术问题，本发明提供了一种原子层沉积制备共掺的氧化 辞薄膜的方法， 包括：  In order to solve the above technical problems, the present invention provides a method for preparing a co-doped oxidized film by atomic layer deposition, comprising:
将基片放入 ALD反应腔室中， 对基片及腔室管道进行加热， 然后依次 进行多组分的复合沉积；  The substrate is placed in an ALD reaction chamber, and the substrate and the chamber tube are heated, and then multi-component composite deposition is sequentially performed;
所述复合沉积包括在第一次辞源沉积后， 分别引入一次包含 111主族 元素 X的施主掺杂源的掺杂沉积、第二次辞源沉积、至少两次氮掺杂源沉积 及至少两次氧源沉积， 形成 N-X-N的共掺； 所述氮掺杂源沉积和所述氧源的 沉积顺序是先氧源沉积， 后氮掺杂源沉积； 所述包含 III主族元素施主掺杂 源沉积与所述第二次辞源沉积顺序是先第二次辞源沉积， 后包含 ΠΙ主族元 素施主掺杂源沉积。  The composite deposition includes doping deposition of a donor dopant source containing 111 main group elements X, second derivation deposition, at least two nitrogen dopant source depositions, and at least two times after deposition of the first source. Oxygen source deposition, forming co-doping of NXN; the nitrogen doping source deposition and the oxygen source deposition sequence are first oxygen source deposition, post-nitrogen dopant source deposition; and the III main group element donor doping source deposition The deposition sequence with the second source is a second source deposition, followed by a donor dopant source deposition of the ruthenium main group element.
本发明提供的原子层沉积制备共掺的氧化辞薄膜的方法， 采用原子层 沉积方法， 利用原子层沉积层层生长的特点，在氧化辞薄膜生长的过程中， 掺入两次受主元素 N和一次 I I I主族施主掺杂元素 X (X可以为 B， Al , In, Ga) ,形成受主 -施主 -受主共掺的氧化辞薄膜。施主和受主的共掺可以降低 体系的马德隆能量， 提高受主元素的掺入量， 有利于氧化辞薄膜的 Ρ型转 变。 本发明制备工艺筒单， 沉积和掺杂过程易于控制， 制备所得共掺氧化 辞薄膜有利于提高氧化辞薄膜 ρ型电学性质的稳定性。  The method for preparing a co-doped oxidized film by atomic layer deposition provided by the present invention adopts an atomic layer deposition method to utilize the characteristics of atomic layer deposition layer growth, and incorporates two acceptor elements N during the growth process of the oxidized film. And a primary host donor doping element X (X may be B, Al, In, Ga) to form an acceptor-donor-acceptor co-doped oxidized film. The co-doping of the donor and the acceptor can reduce the Madron energy of the system, increase the amount of the acceptor element, and facilitate the Ρ-type transformation of the oxidized film. The preparation process of the invention is simple, and the deposition and doping process is easy to control. The prepared co-doped oxidized film is beneficial to improve the stability of the p-type electrical properties of the oxidized film.
附图说明 DRAWINGS
图 1为本发明实施例提供的原子层沉积制备共掺的氧化辞薄膜的方法 的流程图。 1 is a method for preparing a co-doped oxidized film by atomic layer deposition according to an embodiment of the present invention; Flow chart.
具体实施方式 detailed description
参见图 1所示， 本发明提供的原子层沉积制备共掺的氧化辞薄膜的方 法， 包括：  Referring to Figure 1, the present invention provides a method for preparing a co-doped oxidized film by atomic layer deposition, comprising:
将基片做村底前处理， 并放入 ALD腔室；  The substrate is pre-processed and placed in an ALD chamber;
将腔室抽真空， 将村底腔室加热；  Vacuuming the chamber to heat the bottom chamber;
向 ALD腔室中， 引入 Zn(C2H5)2; Introducing Zn(C 2 H 5 ) 2 into the ALD chamber;
用高纯氮气清洗 ALD腔室；  Cleaning the ALD chamber with high purity nitrogen;
向 ALD腔室中， 引入水蒸气；  Introducing water vapor into the ALD chamber;
用高纯氮气清洗 ALD腔室；  Cleaning the ALD chamber with high purity nitrogen;
向 ALD腔室中， 引入氮气等离子体；  Introducing a nitrogen plasma into the ALD chamber;
用高纯氮气清洗 ALD腔室；  Cleaning the ALD chamber with high purity nitrogen;
向 ALD腔室中， 引入 Zn(C2H5)2; Introducing Zn(C 2 H 5 ) 2 into the ALD chamber;
用高纯氮气清洗 ALD腔室；  Cleaning the ALD chamber with high purity nitrogen;
向 ALD腔室中， 引入施主掺杂气源；  Introducing a donor doping gas source into the ALD chamber;
用高纯氮气清洗 ALD腔室；  Cleaning the ALD chamber with high purity nitrogen;
向 ALD腔室中， 引入水蒸气；  Introducing water vapor into the ALD chamber;
用高纯氮气清洗 ALD腔室；  Cleaning the ALD chamber with high purity nitrogen;
向 ALD腔室中， 引入氮气等离子体；  Introducing a nitrogen plasma into the ALD chamber;
用高纯氮气清洗 ALD腔室。 辞薄膜的方法进行说明。  The ALD chamber was purged with high purity nitrogen. The method of the film is explained.
实施例 1 :  Example 1
将硅村底或者玻璃村底用浓硫酸双氧水进行处理， 再用超纯水超声波 进行清洗， N2吹干， 其中浓 酸:双氧水 = 4： 1。 将村底放入原子层沉积的 腔室内， 开启原子层沉积设备， 调整工作参数， 抽真空、 加热沉底， 达到 实验所需各种工作环境； 进行 B-N共掺氧化辞薄膜的多组复合沉积， 即The bottom of the silicon village or the glass substrate is treated with concentrated sulfuric acid hydrogen peroxide, and then ultrasonically washed with ultrapure water, and N2 is blown dry, wherein concentrated acid: hydrogen peroxide = 4:1. Put the bottom of the village into the chamber of the atomic layer deposition, turn on the atomic layer deposition equipment, adjust the working parameters, evacuate, heat the sinking bottom, and reach Various working environments required for the experiment; performing multiple sets of composite deposition of BN co-doped oxidation film, ie
Zn(C2H5)2 I N2 I H20 I N2 /plasma N2 / N2 / Zn(C2H5)2/ N2 I BF31 N2 I H20 I N2 I plasma N2/N2 = 0.15 s / 50 s / 0.07 s / 50 s / 10 s / 50 s / 0.08 s / 50 s/ 0.08 s / 50 s/0.07 s/50 s/ 10 s/50 s。 其中氮气的流量为 1 sccm-1000 sccm, 优选 地为 15 sccm, 进气时间为 0.04 s - 5 s, 优选地为 0.15 s, 清洗时间为 5 s - 150 s, 优选地为 50s, 村底温度为 100°C - 500°C, 优选地为 300°C; 其中等离 子放电功率为 1 W- 100 W, 优选地为 50 W, 放电时间为 I s - 50 s, 优选的 为 10 s。 在此期间通过 N2等离子体来引入 N掺杂， 通过 BF3来提供 B原子， 两次 plasma N2和一次 BF3的沉积， 使得 B在 ZnO中替辞 (ΒΖη) , N替代 O的位 置， 在薄膜中形成 N-Zr-N的复合体， 该复合体可以降低离化能， 促进 p型 电导的形成。 重复该多组分的复合沉积， 可以逐层生长 N-B-N共掺的氧化 辞薄膜。 Zn(C 2 H 5 ) 2 IN 2 IH 2 0 IN 2 /plasma N 2 / N 2 / Zn(C 2 H 5 ) 2 / N 2 I BF 3 1 N 2 IH 2 0 IN 2 I plasma N 2 / N 2 = 0.15 s / 50 s / 0.07 s / 50 s / 10 s / 50 s / 0.08 s / 50 s / 0.08 s / 50 s / 0.07 s / 50 s / 10 s / 50 s. Wherein the flow rate of nitrogen gas is from 1 sccm to 1000 sccm, preferably 15 sccm, the intake time is from 0.04 s to 5 s, preferably 0.15 s, and the cleaning time is from 5 s to 150 s, preferably 50 s, and the substrate temperature It is from 100 ° C to 500 ° C, preferably 300 ° C; wherein the plasma discharge power is from 1 W to 100 W, preferably 50 W, and the discharge time is from 1 s to 50 s, preferably 10 s. During this period, N doping is introduced by N 2 plasma, B atom is supplied by BF 3 , deposition of two plasma N 2 and primary BF 3 is performed, so that B is substituted in ZnO (Β Ζ η ), and N is substituted for O. Forming a complex of N-Zr-N in the film, which can reduce the ionization energy and promote the formation of p-type conductance. By repeating the multicomponent composite deposition, the NBN co-doped oxidized film can be grown layer by layer.
实施例 2:  Example 2:
将硅村底或者玻璃村底用浓硫酸双氧水进行处理， 再用超纯水超声波 进行清洗， N2吹干， 其中浓 酸 ： 双氧水 =4 : 1。 将村底放入原子层沉积 的腔室内， 开启原子层沉积设备， 调整工作参数， 抽真空、 加热沉底， 达 到实验所需各种工作环境； 进行 A1-N共掺氧化辞薄膜的多组复合沉积， 即The bottom of the silicon village or the bottom of the glass is treated with concentrated sulfuric acid hydrogen peroxide, and then ultrasonically washed with ultrapure water, and N 2 is blown dry, wherein concentrated acid: hydrogen peroxide = 4:1. Put the bottom of the village into the chamber of the atomic layer deposition, turn on the atomic layer deposition equipment, adjust the working parameters, vacuum and heat the sinking bottom to achieve various working environments required for the experiment; carry out multiple groups of A1-N co-doped oxidation film Composite deposition, ie
Zn(C2H5)2 I N2 I H2O I N2 I plasma N2 / N2 / Zn(C2H5)2 I N2 I A1(CH3)31 N2 I H20 I N2 I plasma N2/N2 = 0.15 s / 50 s / 0.07 s / 50 s /10 s / 50 s / 0.08 s I 50 s/ 0.08 s/50 s/0.07 s/50 s/ 10 s/50 s。 其中氮气的流量为 1 sccm-1000 sccm, 优选地为 15 sccm, 进气时间为 0.04 s-5 s, 优选地为 0.15 s, 清洗时 间为 5 s - 150 s,优选地为 50s,村底温度为 100°C - 500°C,优选地为 300°C; 其中等离子放电功率为 1W- 100 W,优选地为 50 W,放电时间为 1 s-50s, 优选的为 10 s。 在此期间通过 N2等离子体来引入 N掺杂， 通过 A1(CH3)3来提 供 A1原子， 两次 plasma N2和一次 A1(CH3)3的沉积， 使得 A1在 ZnO中替辞 (Alz„), N替代 0的位置， 在氧化辞薄膜中形成 N-A1-N的共掺， 重复该多组 分的复合沉积， 可以逐层生长 N-A1-N共掺的氧化辞薄膜， 促进 p型电导的 形成。 Zn(C 2 H 5 ) 2 IN 2 I H2O IN 2 I plasma N 2 / N 2 / Zn(C 2 H 5 ) 2 IN 2 I A1(CH 3 ) 3 1 N 2 IH 2 0 IN 2 I plasma N 2 /N 2 = 0.15 s / 50 s / 0.07 s / 50 s /10 s / 50 s / 0.08 s I 50 s / 0.08 s / 50 s / 0.07 s / 50 s / 10 s / 50 s. Wherein the flow rate of nitrogen is from 1 sccm to 1000 sccm, preferably 15 sccm, the intake time is 0.04 s to 5 s, preferably 0.15 s, and the cleaning time is from 5 s to 150 s, preferably 50 s, and the substrate temperature is It is from 100 ° C to 500 ° C, preferably 300 ° C; wherein the plasma discharge power is from 1 W to 100 W, preferably 50 W, and the discharge time is from 1 s to 50 s, preferably 10 s. During this time be introduced by N 2 plasma doping N by A1 (CH 3) 3 to provide A1 atoms, and a N 2 twice Plasma A1 (CH 3) 3 is deposited, so that for speech in ZnO A1 ( Alz„), N replaces the position of 0, forms a co-doping of N-A1-N in the oxidized film, repeats the composite deposition of the multi-component, and can grow the N-A1-N co-doped oxidized film layer by layer. Promote p-type conductance Formed.
实施例 3:  Example 3:
将硅村底或者玻璃村底用浓硫酸双氧水进行处理， 再用超纯水超声波 进行清洗， N2吹干， 其中浓 酸 ： 双氧水 =4 : 1。 将村底放入原子层沉积 的腔室内， 开启原子层沉积设备， 调整工作参数， 抽真空、 加热沉底， 达 到实验所需各种工作环境； 进行 In-N共掺氧化辞薄膜的多组复合沉积， 即 Zn(C2H5)2 I N2 I H20 I N2 I plasma N2 / N2 / Zn(C2H5)2/ N2 I In(CH2CH3)31 N2 I H20 I N2 I plasma N2/N2 = 0.15 s / 50 s / 0.07 s / 50 s /10 s / 50 s / 0.08 s I 50 s/ 0.08 s / 50 s /0.07 s / 50 s / 10 s / 50 s。 其中氮气的流量为 1 sccm-1000 sccm, 优选地为 15 sccm, 进气时间为 0.04 s- 5 s, 优选地为 0.15 s, 清洗时 间为 5 s - 150 s,优选地为 50s,村底温度为 100°C - 500°C,优选地为 300°C; 其中等离子放电功率为 1W- 100 W,优选地为 50 W,放电时间为 1 s-50s, 优选的为 10 s。 在此期间通过 N2等离子体来引入 N掺杂， 通过 In(CH2CH3)3 来提供 In原子， 两次 plasma N2和一次 In(CH2CH3)3的沉积， 使得 In在 ZnO中 替辞 (InZn), N替代 0的位置， 在薄膜中形成 N-In-N的共掺， 重复该多组分 复合沉积， 可以逐层生长 N-In-N共掺的氧化辞薄膜。 共掺有利于提高受主 元素掺杂量， 促进 p型电导的形成。 The bottom of the silicon village or the bottom of the glass is treated with concentrated sulfuric acid hydrogen peroxide, and then ultrasonically washed with ultrapure water, and N 2 is blown dry, wherein concentrated acid: hydrogen peroxide = 4:1. Put the bottom of the village into the chamber of the atomic layer deposition, turn on the atomic layer deposition equipment, adjust the working parameters, vacuum and heat the sinking bottom to achieve the various working environments required for the experiment; perform multiple sets of In-N co-doped oxidation film Composite deposition, ie Zn(C 2 H 5 ) 2 IN 2 IH 2 0 IN 2 I plasma N 2 / N 2 / Zn(C 2 H 5 ) 2 / N 2 I In(CH 2 CH 3 ) 3 1 N 2 IH 2 0 IN 2 I plasma N 2 /N 2 = 0.15 s / 50 s / 0.07 s / 50 s /10 s / 50 s / 0.08 s I 50 s / 0.08 s / 50 s /0.07 s / 50 s / 10 s / 50 s. Wherein the flow rate of nitrogen gas is from 1 sccm to 1000 sccm, preferably 15 sccm, the intake time is from 0.04 s to 5 s, preferably 0.15 s, and the cleaning time is from 5 s to 150 s, preferably 50 s, and the substrate temperature is It is from 100 ° C to 500 ° C, preferably 300 ° C; wherein the plasma discharge power is from 1 W to 100 W, preferably 50 W, and the discharge time is from 1 s to 50 s, preferably 10 s. During this period, N doping is introduced by N 2 plasma, In (CH 2 CH 3 ) 3 is supplied to provide In atoms, and two plasma N 2 and one In (CH 2 CH 3 ) 3 are deposited, so that In is in ZnO. Neutral (In Zn ), N replaces the position of 0, forms N-In-N co-doping in the film, repeats the multi-component composite deposition, and can grow the N-In-N co-doped oxidized film layer by layer. . Co-doping is beneficial to increase the doping amount of the acceptor element and promote the formation of p-type conductance.
实施例 4:  Example 4:
将硅村底或者玻璃村底用浓硫酸双氧水进行处理， 再用超纯水超声波 进行清洗， N2吹干， 其中浓 酸 ： 双氧水 =4 : 1。 将村底放入原子层沉积 的腔室内， 开启原子层沉积设备， 调整工作参数， 抽真空、 加热沉底， 达 到实验所需各种工作环境； 进行 Ga-N共掺氧化辞薄膜的多组复合沉积， 即 The bottom of the silicon village or the glass substrate is treated with concentrated sulfuric acid hydrogen peroxide, and then ultrasonically cleaned with ultrapure water, and N2 is blown dry, wherein concentrated acid: hydrogen peroxide = 4:1. Put the bottom of the village into the chamber of the atomic layer deposition, turn on the atomic layer deposition equipment, adjust the working parameters, vacuum and heat the sinking bottom to achieve the various working environments required for the experiment; carry out the multi-group of Ga-N co-doped oxidation film Composite deposition, ie
Zn(C2H5)2 I N2 I H2O I N2 I plasma N2 / N2 / Zn(C2H5)2 / N2 / Ga (CH2CH3)31 N2 I H20 I N2 I plasma N2/ N2 = 0.15 s / 50 s / 0.07 s / 50 s / 10 s / 50 s / 0.08 s I 50 s/0.08 s/50 s/0.07 s/50 s/10 s/50 s。 其中氮气的流量为 1 sccm-1000 sccm, 优选地为 15 sccm, 进气时间为 0.04 s - 5 s, 优选地为 0.15 s, 清洗时 间为 5 s - 1500 s, 优选地为 50 s, 村底温度为 100°C - 500°C, 优选地为 300 °C ; 其中等离子放电功率为 1 W - 100 W, 优选地为 50 W, 放电时间为 1 s - 50 s , 优选的为 10 s。 在此期间通过 N2等离子体来引入 N掺杂， 通过 Zn(C 2 H 5 ) 2 IN 2 I H2O IN 2 I plasma N 2 / N 2 / Zn(C 2 H 5 ) 2 / N 2 / Ga (CH 2 CH 3 ) 3 1 N 2 IH 2 0 IN 2 I plasma N 2 / N 2 = 0.15 s / 50 s / 0.07 s / 50 s / 10 s / 50 s / 0.08 s I 50 s / 0.08 s / 50 s / 0.07 s / 50 s / 10 s / 50 s. Wherein the flow rate of nitrogen is from 1 sccm to 1000 sccm, preferably 15 sccm, the intake time is from 0.04 s to 5 s, preferably 0.15 s, and the cleaning time is from 5 s to 1500 s, preferably 50 s. The temperature is from 100 ° C to 500 ° C, preferably 300 ° C ; wherein the plasma discharge power is 1 W - 100 W, preferably 50 W, and the discharge time is 1 s - 50 s, preferably 10 s. Introducing N-doping through the N2 plasma during this period,
Ga(CH2CH3)3来提供 Ga原子， 两次 plasma N2和一次 Ga(CH2CH3)3的沉积，使 得 Ga在 ZnO中替辞 (GaZn) , N替代 0的位置，在薄膜中形成 N-Ga-N的的共掺， 重复该多组分的复合沉积， 可以逐层生长 N-Ga-N共掺的氧化辞薄膜。 共掺 有利于提高受主元素掺杂量， 促进 p型电导的形成。 辞薄膜， 在此期间通过 N2等离子体来生成 N原子， 通过 III主族元素气源来 提供施主掺杂原子， 两次 plasma N2和一次施主掺杂源的沉积， 使得 ΠΙ主族 施主掺杂元素 X(X可以为 B, Al, In, Ga)在 ZnO中替辞 (XZn) , N替代 O的位置， 在薄膜中形成 N-X-N的的共掺， 共掺可以降低离化能， 有利于提高受主元 素掺杂量，促进 p型电导的形成。重复该多组复合沉积，可以逐层生长 N-X-N 共掺的氧化辞薄膜。 Ga(CH 2 CH 3 ) 3 is used to provide Ga atoms, two depositions of plasma N 2 and one time of Ga(CH 2 CH 3 ) 3 , such that Ga replaces (Ga Zn ) in ZnO, and N replaces the position of 0. The co-doping of N-Ga-N is formed in the film, and the multi-component composite deposition is repeated, and the N-Ga-N co-doped oxidized film can be grown layer by layer. Co-doping is beneficial to increase the doping amount of the acceptor element and promote the formation of p-type conductance. The film, during which N atoms are generated by N 2 plasma, the donor dopant atoms are provided by the III main group gas source, and the deposition of the two plasma N 2 and the primary donor doping source causes the bismuth main donor to be doped The heteroelement X (X can be B, Al, In, Ga) in ZnO (X Zn ), N replaces the position of O, forms co-doping of NXN in the film, co-doping can reduce the ionization energy, It is beneficial to increase the doping amount of the acceptor element and promote the formation of p-type conductance. By repeating the multiple sets of composite deposits, the NXN co-doped oxidized film can be grown layer by layer.
本发明提供的方法能够实现 ΠΙ主族施主掺杂元素 X(X可以为 B, Al, In, Ga)与 N元素的共掺，而且方法筒单，利用原子层沉积单层循环生长的特点， 在氧化辞薄膜生长的过程中实现均匀的在整个薄膜结构中进行掺杂，施主- 受主共掺后的氧化辞薄膜， 可以降低体系饿马德隆能， 增加 N的掺杂浓度， 亦可以得到更浅的受主能级， 有利于促进 p型电导的形成。  The method provided by the invention can realize the co-doping of the doping element X (X can be B, Al, In, Ga) with the N element of the main group of the ruthenium, and the method is simple, and the characteristics of the single layer circulation growth by atomic layer deposition are adopted. In the process of oxidizing the film growth, uniform doping in the whole film structure, donor-acceptor co-doping oxidized film can reduce the system's hungry madron energy, increase the doping concentration of N, and also get more The shallow acceptor level is conducive to the formation of p-type conductance.
而非限制， 尽管参照实例对本发明进行了详细说明， 本领域的普通技术人 员应当理解， 可以对本发明的技术方案进行修改或者等同替换， 而不脱离 本发明技术方案的精神和范围，其均应涵盖在本发明的权利要求范围当中。 The present invention has been described in detail with reference to the accompanying drawings, and the embodiments of the invention It is intended to be included within the scope of the appended claims.

Claims

权 利 要 求 书 claims
1、 一种原子层沉积制备共掺的氧化辞薄膜的方法， 其特征在于， 包 括： 1. A method for preparing a co-doped oxide film by atomic layer deposition, which is characterized by including:
将基片放入 ALD反应腔室中， 对基片及腔室管道进行加热， 然后进行 多组分的复合沉积； Place the substrate into the ALD reaction chamber, heat the substrate and chamber pipes, and then perform multi-component composite deposition;
所述复合沉积包括在第一次辞源沉积后， 分别引入一次包含 111主族 元素 X的施主掺杂源的掺杂沉积、第二次辞源沉积、至少两次氮掺杂源沉积 及至少两次氧源沉积， 形成 N-X-N的共掺； 所述氮掺杂源沉积和所述氧源的 沉积顺序是先氧源沉积， 后氮掺杂源沉积； 所述包含 III主族元素施主掺杂 源沉积与所述第二次辞源沉积顺序是先第二次辞源沉积， 后包含 ΠΙ主族元 素施主掺杂源沉积。 The composite deposition includes, after the first source deposition, introducing a doping deposition of a donor doping source including 111 main group element X, a second source deposition, at least two nitrogen doping source depositions and at least two Oxygen source deposition to form N-X-N co-doping; The nitrogen doping source deposition and the oxygen source deposition sequence are oxygen source deposition first, then nitrogen doping source deposition; The donor doping source containing III main group elements is deposited The sequence of the second source deposition is first the second source deposition, and then the donor doping source including the II main group element is deposited.
2、 根据权利要求 1所述的制备方法， 其特征在于， 所述基片为经浓硫 酸和双氧水处理， 并经超纯水超声过的硅片、 蓝宝石或玻璃， 村底表面带 有羟基。 2. The preparation method according to claim 1, characterized in that the substrate is a silicon wafer, sapphire or glass that has been treated with concentrated sulfuric acid and hydrogen peroxide and ultrasonicated with ultrapure water, and has hydroxyl groups on the bottom surface.
3、根据权利要求 2所述的制备方法，其特征在于，所述复合沉积包括： 在真空环境下依次用第一次辞源、 氧源、 氮掺杂源、 第二次辞源、 包 含 I I I主族元素 X的施主掺杂源、 氧源和氮掺杂源进行沉积得到受主-施主- 受主共掺的 ZnO薄膜， 所述第一次辞源、 氮掺杂源、 氧源、 包含 I I I主族元 素 X的施主掺杂源及第二次辞源在沉积室内暴露时间依次为 0.15 s、 10 s、 0.07 s、 0.08 s、 0.08 s。 3. The preparation method according to claim 2, characterized in that the composite deposition includes: sequentially using a first source, an oxygen source, a nitrogen doping source, a second source, including the III main group in a vacuum environment The donor doping source, oxygen source and nitrogen doping source of element The exposure times of the donor doping source and the second source of element X in the deposition chamber are 0.15 s, 10 s, 0.07 s, 0.08 s, and 0.08 s respectively.
4、 根据权利要求 3所述的制备方法， 其特征在于， 在每次沉积之后采 用高纯氮气清洗沉积室， 清洗时间为 50s。 4. The preparation method according to claim 3, characterized in that, after each deposition, high-purity nitrogen gas is used to clean the deposition chamber, and the cleaning time is 50 s.
5、 根据权利要求 1所述的制备方法， 其特征在于， 所述辞源是含辞的 烷基化合物或含辞的 化物， 所述氧源是水蒸汽或氧气等离子体； 所述氮 掺杂源为 N20、 N2、 NO、 NO2或 NH3等离子体。 5. The preparation method according to claim 1, characterized in that, the source is an alkyl compound or an alkyl compound, the oxygen source is water vapor or oxygen plasma; the nitrogen doping source It is N 2 0, N 2 , NO, NO2 or NH 3 plasma.
6、 根据权利要求 5所述的制备方法， 其特征在于， 6. The preparation method according to claim 5, characterized in that,
含辞的 化物是氯化辞 ZnCh, 所述含辞的烷基化合物是二乙基辞 Zn(C2H5)2或二甲基辞 Zn(CH3)2。 The neutral compound is ZnCh chloride, and the neutral alkyl compound is diethyl Zn(C 2 H 5 ) 2 or dimethyl Zn(CH 3 ) 2 .
7、 根据权利要求 5所述的制备方法， 其特征在于， 所述包含 III主族元 素 X的施主掺杂源是含 X的 化物、 含 X的醇化物、 含 X的烷基化物、 含 X 的氢化物、 含 X的环戊二烯基、 含 X的烷酰胺或含 X的脒基。 7. The preparation method according to claim 5, characterized in that the donor doping source containing the main group III element X is an X-containing compound, an X-containing alcoholate, an X-containing alkylate, or an X-containing alkylate. hydride, X-containing cyclopentadienyl group, X-containing alkamide group or X-containing amidine group.
8、 根据权利要求 5所述的制备方法， 其特征在于， 所述含 X的卤化物 是三氟化硼 BF3, 所述含 X的醇化物是甲醇硼 B(OCH3)3), 所述含 X的烷基化 物是三甲基铝 A1(CH3)3、 三乙基铟 In(CH2CH3)3或三乙基镓 Ga(CH2CH3)3。 8. The preparation method according to claim 5, wherein the X-containing halide is boron trifluoride BF 3 , and the X-containing alcoholate is boron methoxide B (OCH 3 ) 3 ), so The X-containing alkylate is trimethylaluminum A1(CH 3 ) 3 , triethyl indium In(CH 2 CH 3 ) 3 or triethyl gallium Ga(CH 2 CH 3 ) 3 .
9、 根据权利要求 5述的制备方法， 其特征在于， 还包括： 9. The preparation method according to claim 5, further comprising:
通过控制所述的氮掺杂源与水蒸气的通气时间来调节掺杂氧化辞薄 膜中氮掺杂源与氧的比例。 The ratio of the nitrogen doping source and oxygen in the doped oxide film is adjusted by controlling the ventilation time of the nitrogen doping source and water vapor.
10、 根据权利要求 5所述的制备方法， 其特征在于， 还包括： 通过控制 III主族元素掺杂源与辞源的通气时间来调节掺杂氧化辞薄 膜中施主掺杂与辞的比例。 10. The preparation method according to claim 5, further comprising: adjusting the ratio of donor doping and doping in the doped oxide film by controlling the ventilation time of the III main group element doping source and the source.
PCT/CN2012/086981 2012-12-11 2012-12-20 Method for preparing co-doped zinc oxide thin film through atomic layer deposition WO2014089864A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201210532025.7A CN103866276B (en) 2012-12-11 2012-12-11 The method of the zinc-oxide film that ald preparation is co-doped with
CN201210532025.7 2012-12-11

Publications (1)

Publication Number Publication Date
WO2014089864A1 true WO2014089864A1 (en) 2014-06-19

Family

ID=50905271

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2012/086981 WO2014089864A1 (en) 2012-12-11 2012-12-20 Method for preparing co-doped zinc oxide thin film through atomic layer deposition

Country Status (2)

Country Link
CN (1) CN103866276B (en)
WO (1) WO2014089864A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105779971A (en) * 2016-02-01 2016-07-20 中国科学院嘉兴微电子仪器与设备工程中心 Method for depositing p-type semi-conductor zinc oxide film on atomic layer

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1542915A (en) * 2003-11-04 2004-11-03 浙江大学 p-Zn1-XMgXO crystal film and method for making same
JP2007220818A (en) * 2006-02-15 2007-08-30 Kochi Prefecture Sangyo Shinko Center Thin-film transistor and manufacturing method thereof
WO2007117158A1 (en) * 2006-04-07 2007-10-18 Institute Of Geological And Nuclear Sciences Limited Zinc oxide materials and methods for their preparation
CN101760726A (en) * 2009-12-31 2010-06-30 华南师范大学 Preparation method of B and N codope ZnO film
CN102304700A (en) * 2011-09-23 2012-01-04 中国科学院微电子研究所 Preparation method of nitrogen-doped zinc oxide film

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7972898B2 (en) * 2007-09-26 2011-07-05 Eastman Kodak Company Process for making doped zinc oxide
CN101540354A (en) * 2008-02-29 2009-09-23 陈敏璋 Zinc oxide based semiconductor luminous component and manufacturing method thereof
KR20110139394A (en) * 2010-06-23 2011-12-29 주성엔지니어링(주) Thin film transistor and method of manufacturing the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1542915A (en) * 2003-11-04 2004-11-03 浙江大学 p-Zn1-XMgXO crystal film and method for making same
JP2007220818A (en) * 2006-02-15 2007-08-30 Kochi Prefecture Sangyo Shinko Center Thin-film transistor and manufacturing method thereof
WO2007117158A1 (en) * 2006-04-07 2007-10-18 Institute Of Geological And Nuclear Sciences Limited Zinc oxide materials and methods for their preparation
CN101760726A (en) * 2009-12-31 2010-06-30 华南师范大学 Preparation method of B and N codope ZnO film
CN102304700A (en) * 2011-09-23 2012-01-04 中国科学院微电子研究所 Preparation method of nitrogen-doped zinc oxide film

Also Published As

Publication number Publication date
CN103866276B (en) 2016-08-03
CN103866276A (en) 2014-06-18

Similar Documents

Publication Publication Date Title
CN104988579A (en) Gallium oxide film based on sapphire substrate and growing method of gallium oxide film
CN103456603B (en) Gallium system heterogeneous semiconductor substrate is prepared method and the gallium oxide film of gallium oxide film
CN104087909A (en) Preparation method of cubic silicon carbide film
CN104962858A (en) GaAs substrate-based gallium oxide thin film and growing method thereof
WO2012116477A1 (en) Preparation method of high density zinc oxide nanometer granules
CN103866277B (en) Method for preparing double-acceptor co-doped zinc oxide thin film through atomic layer deposition
CN105118853A (en) MgO substrate-based gallium oxide thin film and growing method thereof
US20140287550A1 (en) Plasma enhanced thermal evaporator
WO2014089864A1 (en) Method for preparing co-doped zinc oxide thin film through atomic layer deposition
CN103866268B (en) Donor-acceptor based on nitrogen is co-doped with the preparation method of zinc-oxide film
CN104561940A (en) Plasma-assisted metal-organic chemical vapor deposition equipment and method
JP6387264B2 (en) Method for manufacturing p-type ZnO-based semiconductor layer and method for manufacturing ZnO-based semiconductor element
CN103866269A (en) Method for preparing Te-N co-doped zinc oxide thin film through atomic layer deposition
CN103866275B (en) The preparation method being co-doped with zinc-oxide film of ald
CN103866280B (en) A kind of ald prepares the method that donor-acceptor is co-doped with zinc-oxide film
KR100803950B1 (en) Preparation of p-zno film by plasma enhanced metal-organic chemical vapor deposition
CN104451867A (en) Method for preparing high-quality ZnMgBeO film
CN103866272B (en) For the method improving zinc-oxide film P type stability
CN103866271B (en) For the preparation method that donor-acceptor is co-doped with zinc-oxide film
CN103866270B (en) The preparation method of zinc-oxide film it is co-doped with for Te-N
CN103866279B (en) The method that ald prepares the zinc-oxide film that N As are co-doped with
US8722456B2 (en) Method for preparing p-type ZnO-based material
CN103866289B (en) A kind of P N are co-doped with the preparation method of zinc-oxide film
CN103866267A (en) Preparation method for N-Zr co-doping of zinc oxide thin film
CN103866265B (en) Double acceptor based on nitrogen is co-doped with the preparation method of zinc-oxide film

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12889886

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12889886

Country of ref document: EP

Kind code of ref document: A1