CN105525349A - Cuprous oxide single crystal thin film preparation method - Google Patents
Cuprous oxide single crystal thin film preparation method Download PDFInfo
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- CN105525349A CN105525349A CN201511025986.9A CN201511025986A CN105525349A CN 105525349 A CN105525349 A CN 105525349A CN 201511025986 A CN201511025986 A CN 201511025986A CN 105525349 A CN105525349 A CN 105525349A
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
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Abstract
The present invention discloses a cuprous oxide single crystal thin film preparation method comprising the following steps: step 1, a copper source is put into a reaction boat, the reaction boat is placed into a quartz reaction tube; step 2, a substrate after cleaning, and by blow-drying is placed on a substrate holder, and then placed into the quartz reaction tube; step 3, a copper source gas path is opened, an inert gas enters the quartz reaction tube through the reaction boat, and an outlet of the reaction boat directly faces the surface of the substrate; step 4, an oxygen source gas path is opened, an inert gas carrying an oxygen source enters the quartz reaction tube; step 5, the quartz reaction tube is heated, and the reaction boat and the substrate in the quartz reaction tube are heated; and step 6, the reaction temperature of the reaction boat and the substrate is adjusted, the growth time is set, a cuprous oxide film is deposited on the substrate to complete the preparation. The cuprous oxide single crystal thin film preparation method can greatly reduce the production cost of the cuprous oxide film.
Description
Technical field
The invention belongs to technical field of semiconductors, be specifically related to a kind of preparation method of cuprous oxide film.
Background technology
The energy gap of Red copper oxide is 2.2eV, is within the scope of the best energy gap of photovoltaic generation, matches with the maximum value of solar spectrum.In theory, the photoelectric transformation efficiency of Red copper oxide solar cell can reach more than 20%.According to estimates, as long as can reach the photoelectric transformation efficiency of 5%, Red copper oxide application on the solar cell just has higher economic worth.And, copper raw material aboundresources, cheap, nontoxic pollution-free.These all show that cuprous oxide film has huge potential using value in sun power.
The technology preparing Red copper oxide film is a lot, and almost capsule contains all conventional film growth techniques, as: electrochemical process, magnetron sputtering method, thermal oxidation method, pulsed laser deposition technique, sol-gel method, chemical vapour deposition technique, Metalorganic chemical vapor deposition technology etc.
But the cuprous oxide film obtained at present is mostly polycrystalline or amorphous, and is wherein easily mixed into cupric oxide phase.Wherein the measured cuprous oxide film of crystalline all adopts MOCVD method or MBE method to prepare, not only there is the problem of equipment and organometallic sources expensive starting materials, also need the rare magnesium oxide substrate using unstable chemcial property, or with magnesium oxide as substrate (see FuYajun, LeiHongwei, WangXuemin, YanDawei, CaoLinhong, YaoGang, ShenChangle, PengLiping, ZhaoYan, WangYuying, WuWeidong, Appl.Surf.S.273 (2013) 19.) and cuprous oxide film between interposed layer (see LiJunqiang, MeiZengxia, YeDaqian, LiangHuili, LiuYaoping, DuXiaolong.J.Cryst.Cr.351 (2012) 63.).
Summary of the invention
(1) technical problem that will solve
The object of the present invention is to provide a kind of method for manufacturing thin film of Red copper oxide, by adopting industrial raw material cuprous iodide cheap and easy to get as raw material, select commercial Sapphire Substrate or silicon substrate, prepare cuprous oxide film by vapor deposition reaction in atmospheric conditions.
(2) technical scheme
The present invention proposes a kind of preparation method of cuprous oxide film, comprises the steps: step 1, and Jiang Tongyuan puts into reaction boat, and crystal reaction tube put into by reaction boat; Step 2, is placed on substrate bracket by the substrate after cleaning, drying up, puts into crystal reaction tube; Step 3, opens copper source gas circuit, and allow rare gas element enter crystal reaction tube by reaction boat, the outlet of reaction boat is just to substrate surface; Step 4, opens oxygen source gas circuit, allows rare gas element carry oxygen source and enters crystal reaction tube; Step 5, heated quartz reaction tubes, the reaction boat in heated quartz reaction tubes and substrate; Step 6, regulates the working temperature of reaction boat and substrate, and setting growth time, at deposited on substrates cuprous oxide film, completes preparation.
Preferably, described copper source is cuprous iodide.
Preferably, described substrate is sapphire or silicon substrate.
Preferably, described oxygen source is the mixed gas of a kind of oxygen-containing gas or multiple oxygen-containing gas.
Preferably, described rare gas element is nitrogen, argon gas, helium or neon, or its mixed inert gas.
Preferably, described copper source gas circuit and oxygen source gas circuit are independent separately, start in the outlet oxygen source gas circuit and copper source gas circuit of reacting boat mixing of meeting.
Preferably, the outlet distance substrate surface 0.5cm-5cm of boat is reacted.
Preferably, the working temperature of substrate is at 700 DEG C ~ 1100 DEG C.
Preferably, the working temperature of substrate is at 750 DEG C ~ 950 DEG C.
(3) beneficial effect
Beneficial aspects of the present invention is: equipment requirements used is simple, do not need expensive vacuum apparatus, do not need expensive raw material, do not need rare substrate material or interposed layer material, do not need any particular energy source as plasma body, laser class, there are large industrial potentiality.
Accompanying drawing explanation
Fig. 1 is the XRD diffractogram of the cuprous oxide film prepared on a sapphire substrate;
Fig. 2 is the transmission electron microscope picture of the cuprous oxide film prepared on a sapphire substrate;
Fig. 3 is the XRD diffractogram of the cuprous oxide film prepared on a silicon substrate;
Fig. 4 is the XRD diffractogram of the cuprous oxide film prepared on a sapphire substrate.
Embodiment
For making the object, technical solutions and advantages of the present invention clearly understand, below in conjunction with specific embodiment, and with reference to accompanying drawing, the present invention is described in more detail.
The present invention proposes a kind of preparation method of cuprous oxide film, comprises step:
Step 1, Jiang Tongyuan puts into reaction boat, and crystal reaction tube put into by reaction boat.Copper source is cuprous iodide.
Step 2, is placed on substrate bracket by the substrate after cleaning, drying up, puts into crystal reaction tube.Wherein substrate is sapphire or silicon substrate.
Step 3, opens copper source gas circuit, and allow rare gas element enter crystal reaction tube by reaction boat, the outlet of reaction boat is just to substrate surface.
Step 4, opens oxygen source gas circuit, allows rare gas element carry oxygen source and enters crystal reaction tube.Oxygen source is the mixed gas of a kind of oxygen-containing gas or multiple oxygen-containing gas, and oxygen-containing gas can be oxygen, water vapour, nitrous oxide, nitrogen protoxide or nitrogen peroxide etc.Rare gas element is nitrogen, argon gas, helium or neon, or its mixed inert gas.Copper source gas circuit and oxygen source gas circuit are independent separately, start in the outlet oxygen source gas circuit and copper source gas circuit of reacting boat mixing of meeting.
Step 5, heated quartz reaction tubes, the reaction boat in heated quartz reaction tubes and substrate.The working temperature of silica tube must not higher than 1100 DEG C, and the working temperature of substrate also must not higher than 1100 DEG C.The outlet distance substrate surface 0.5cm-5cm of reaction boat.
Step 6, regulates the working temperature of reaction boat and substrate, and setting growth time, at deposited on substrates cuprous oxide film, completes preparation.The working temperature of substrate at 700 DEG C ~ 1100 DEG C, preferably at 750 DEG C ~ 950 DEG C.
Fig. 1 is the XRD diffractogram of the cuprous oxide film prepared on a sapphire substrate; Fig. 2 is the transmission electron microscope picture of the cuprous oxide film prepared on a sapphire substrate; Fig. 3 is the XRD diffractogram of the cuprous oxide film prepared on a silicon substrate; Fig. 4 is the XRD diffractogram of the cuprous oxide film prepared on a sapphire substrate.Powder x-ray diffraction (XRD) and transmissioning electric mirror test are used for detecting the crystal orientation of cuprous oxide film and the crystalline quality of preparation.
Below that several cuprous oxide films that experimentally result provides prepare example.
Example 1
Cuprous iodide powder is put into reaction boat as copper source, crystal reaction tube put into by reaction boat; C surface sapphire substrate after cleaning, drying up is placed on substrate bracket, puts into crystal reaction tube; Crystal reaction tube is entered by reaction boat, the outlet distance substrate 0.5cm of reaction boat using nitrogen as carrier gas; Water-bath bubbling bottle using nitrogen as carrier gas by 50 DEG C enters crystal reaction tube; Heated quartz reaction tubes, reaction boat and substrate; The temperature of reaction boat is set in 650 DEG C, and substrate temperature is set as 700 DEG C, and growth 10min, at deposited on substrates cuprous oxide film.As can be seen from the powder XRD pattern of Fig. 1, only have the signal in Red copper oxide crystal orientation, there is no cupric oxide crystalline phase.
Example 2
Cuprous iodide powder is put into reaction boat as copper source, crystal reaction tube put into by reaction boat; C surface sapphire substrate after cleaning, drying up is placed on substrate bracket, puts into crystal reaction tube; Crystal reaction tube is entered by reaction boat, the outlet distance substrate 1cm of reaction boat using argon gas as carrier gas; Crystal reaction tube is entered as carrier gases dilute oxygen using nitrogen; Heated quartz reaction tubes, reaction boat and substrate; The temperature of reaction boat is set in 700 DEG C, and substrate temperature is set as 750 DEG C, and growth 10min, at deposited on substrates cuprous oxide film.Can see from the transmission electron microscope diffraction spectra of Fig. 2, hexagonal sapphire diffraction pattern and foursquare Red copper oxide diffraction pattern, diffraction pattern is shown as Red copper oxide monocrystalline.
Example 3
Cuprous iodide powder is put into reaction boat as copper source, crystal reaction tube put into by reaction boat; Silicon substrate after cleaning, drying up is placed on substrate bracket, puts into crystal reaction tube; Crystal reaction tube is entered by reaction boat, the outlet distance substrate 3cm of reaction boat using helium as carrier gas; Crystal reaction tube is entered as carrier gases dilute nitric oxide using helium; Heated quartz reaction tubes, reaction boat and substrate; The temperature of reaction boat is set in 850 DEG C, and substrate temperature is set as 950 DEG C, and growth 10min, at deposited on substrates cuprous oxide film.Can see from the XRD figure spectrum of Fig. 3, the signal of Red copper oxide is very strong, cover the signal of silicon substrate, and do not have cupric oxide crystalline phase to occur, three diffraction peaks wherein correspond respectively to (110) crystal orientation of Red copper oxide, (220) crystal orientation and (330) crystal orientation, be shown as monocrystalline cuprous oxide film.
Example 4
Cuprous iodide powder is put into reaction boat as copper source, crystal reaction tube put into by reaction boat; Sapphire Substrate after cleaning, drying up is placed on substrate bracket, puts into crystal reaction tube; Crystal reaction tube is entered by reaction boat, the outlet distance substrate 5cm of reaction boat using neon as carrier gas; Crystal reaction tube is entered as carrier gases dilute nitrogen peroxide using neon; Heated quartz reaction tubes, reaction boat and substrate; The temperature of reaction boat is set in 700 DEG C, and substrate temperature is set as 1100 DEG C, and growth 10min, at deposited on substrates cuprous oxide film.Can see, although the signal of Red copper oxide is on the weak side, also not having cupric oxide crystalline phase to occur from the XRD figure spectrum of Fig. 4.
As previously mentioned, application technical solution of the present invention is for the preparation of cuprous oxide film, but be not limited only to this, also comprise by adding doped element for the preparation of doping cuprous oxide film, by changing growth conditions for the preparation of nanometer low-dimensional form, comprise the Red copper oxide of superlattice, quantum dot, quantum wire, quantum well structure.
The method for manufacturing thin film of Red copper oxide provided by the invention, by adopting industrial raw material cuprous iodide cheap and easy to get as raw material, selecting commercial Sapphire Substrate or silicon substrate, preparing cuprous oxide film in atmospheric conditions by vapor deposition reaction.By controlling the scope of growth temperature, inhibit the appearance of cupric oxide crystalline phase.By Optimal Growing condition, monocrystalline cuprous oxide film can be prepared.
Above-described specific embodiment; object of the present invention, technical scheme and beneficial effect are further described; be understood that; the foregoing is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. a preparation method for cuprous oxide film, is characterized in that, comprises the steps:
Step 1, Jiang Tongyuan puts into reaction boat, and crystal reaction tube put into by reaction boat;
Step 2, is placed on substrate bracket by the substrate after cleaning, drying up, puts into crystal reaction tube;
Step 3, opens copper source gas circuit, and allow rare gas element enter crystal reaction tube by reaction boat, the outlet of reaction boat is just to substrate surface;
Step 4, opens oxygen source gas circuit, allows rare gas element carry oxygen source and enters crystal reaction tube;
Step 5, heated quartz reaction tubes, the reaction boat in heated quartz reaction tubes and substrate;
Step 6, regulates the working temperature of reaction boat and substrate, and setting growth time, at deposited on substrates cuprous oxide film, completes preparation.
2. the preparation method of cuprous oxide film as claimed in claim 1, it is characterized in that, described copper source is cuprous iodide.
3. the preparation method of cuprous oxide film as claimed in claim 1, it is characterized in that, described substrate is sapphire or silicon substrate.
4. the preparation method of cuprous oxide film as claimed in claim 1, it is characterized in that, described oxygen source is the mixed gas of a kind of oxygen-containing gas or multiple oxygen-containing gas.
5. the preparation method of cuprous oxide film as claimed in claim 1, it is characterized in that, described rare gas element is nitrogen, argon gas, helium or neon, or its mixed inert gas.
6. the preparation method of cuprous oxide film as claimed in claim 1, is characterized in that, described copper source gas circuit and oxygen source gas circuit are independent separately, starts in the outlet oxygen source gas circuit and copper source gas circuit of reacting boat mixing of meeting.
7. the preparation method of cuprous oxide film as described in claim 1 or 6, is characterized in that, the outlet distance substrate surface 0.5cm-5cm of reaction boat.
8. the preparation method of cuprous oxide film as claimed in claim 1, it is characterized in that, the working temperature of substrate is at 700 DEG C ~ 1100 DEG C.
9. the preparation method of cuprous oxide film as claimed in claim 1, it is characterized in that, the working temperature of substrate is at 750 DEG C ~ 950 DEG C.
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| CN201511025986.9A CN105525349B (en) | 2015-12-31 | 2015-12-31 | A kind of preparation method of cuprous oxide monocrystal thin films |
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| CN201511025986.9A CN105525349B (en) | 2015-12-31 | 2015-12-31 | A kind of preparation method of cuprous oxide monocrystal thin films |
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| CN105525349A true CN105525349A (en) | 2016-04-27 |
| CN105525349B CN105525349B (en) | 2018-09-07 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101058484A (en) * | 2007-03-28 | 2007-10-24 | 杭州电子科技大学 | P-type nitrogen-doping cuprous oxide thin film material and preparation method thereof |
| CN101774629A (en) * | 2010-01-06 | 2010-07-14 | 华中师范大学 | Controllable preparation method of p-type and n-type cuprous oxide film by using hydrothermal method |
| CN102623521A (en) * | 2011-01-31 | 2012-08-01 | 中国科学院物理研究所 | Method for preparing cuprous oxide film |
| CN102732928A (en) * | 2012-07-18 | 2012-10-17 | 西北工业大学 | Preparation method of cuprous oxide semiconductor film material |
| CN103132144A (en) * | 2011-11-23 | 2013-06-05 | 中国科学院物理研究所 | Method for preparing Cu2O film |
-
2015
- 2015-12-31 CN CN201511025986.9A patent/CN105525349B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101058484A (en) * | 2007-03-28 | 2007-10-24 | 杭州电子科技大学 | P-type nitrogen-doping cuprous oxide thin film material and preparation method thereof |
| CN101774629A (en) * | 2010-01-06 | 2010-07-14 | 华中师范大学 | Controllable preparation method of p-type and n-type cuprous oxide film by using hydrothermal method |
| CN102623521A (en) * | 2011-01-31 | 2012-08-01 | 中国科学院物理研究所 | Method for preparing cuprous oxide film |
| CN103132144A (en) * | 2011-11-23 | 2013-06-05 | 中国科学院物理研究所 | Method for preparing Cu2O film |
| CN102732928A (en) * | 2012-07-18 | 2012-10-17 | 西北工业大学 | Preparation method of cuprous oxide semiconductor film material |
Non-Patent Citations (1)
| Title |
|---|
| HIROKI KOBAYASHI，ET AL.: ""Preparation of Cu2O films on MgO(110) substrate by means of halide chemical vapor deposition under atmospheric pressure"", 《MATERIALS CHEMISTRY AND PHYSICS》 * |
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