CN100375253C - Metallorganics chemical vapour deposition (CVD) preparing method for p-type ZnO thin film - Google Patents
Metallorganics chemical vapour deposition (CVD) preparing method for p-type ZnO thin film Download PDFInfo
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- CN100375253C CN100375253C CNB2005100469068A CN200510046906A CN100375253C CN 100375253 C CN100375253 C CN 100375253C CN B2005100469068 A CNB2005100469068 A CN B2005100469068A CN 200510046906 A CN200510046906 A CN 200510046906A CN 100375253 C CN100375253 C CN 100375253C
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Abstract
The present invention relates to a preparation method of metallorganics chemical vapour deposition of a p-type ZnO thin film, which belongs to the technical field of a semiconductor light emitting device and a preparation method thereof and relates to a technological method using a metallorganics chemical vapor deposition (MOCVD) equipment system to grow a p-type ZnO thin film. The present invention is characterized in that doping source gas NO is input into a radio frequency plasma generator from a doping source gas channel, the radio frequency power is adjusted to start, and the doping source gas NO enters a reaction chamber after ionization; a tray of a substrate is adjusted to rotate, and the growth temperature is from 250 to 650 DEG C.; the flow of Zn source carrying gas Ar is from 1 to 10 scm, and oxygen flow is from 10 to 500 sccm; the Zn source carrying gas Ar and the oxygen are fed in the reaction chamber to carry out the growth of the ZnO film. The present invention has the effects and benefits that the present invention provides a technological method for growing a p-type ZnO thin film by MOVCD equipment which is suitable for commercial production, the problem of difficult preparation of the p-type ZnO thin film is overcome, and further an electrical inlet PN junction type ZnO photoconduction device can be prepared.
Description
Technical field
The invention belongs to light emitting semiconductor device and preparation method thereof technical field, particularly relate to the process of a kind of employing metal-organic chemical vapor deposition equipment (MOCVD) device systems growing P-type ZnO film.
Background technology
The blue green light luminous tube commercialization of GaN based material, and application prospect is widely arranged in the solid-state illumination field.The band gap of ZnO and GaN and lattice constant are very approaching, and close photoelectric characteristic is arranged.And ZnO also has some characteristic more superior than GaN, as: have that the gain of higher fusing point and exciton bind energy, exciton is higher, epitaxial growth temperature is low, cost is low, an easy etching and make subsequent process processing more convenient or the like.Therefore, if ZnO luminous tube, laser etc. are succeeded in developing and might be replaced or part replaces the GaN photoelectric device.Particularly ZnO purple, ultraviolet light photo device more people pay attention to.But, usually the ZnO of growth owing to nonstoichiometry than having oxygen room and gap zinc atom, make material be the n type.Producing of p type ZnO just becomes the difficult point that development electricity injection p-n junction type ZnO photoelectric device must solve like this.
At present, the method of growing ZnO thin-film is a lot, and pulsed laser deposition (PLD), molecular beam epitaxy (MBE), metal-organic chemical vapor deposition equipment (MOCVD), sputter (Sputtering), electron beam evaporation, spray pyrolysis and collosol and gel methods such as (Sol-gel) are arranged.Because the MOCVD method is fit to suitability for industrialized production, so the present invention will solve MOCVD method growing P-type ZnO thin-film technique problem.
Summary of the invention
The purpose of this invention is to provide the process that a kind of usefulness is fit to the MOCVD equipment growing P-type ZnO film of suitability for industrialized production, overcome the problem that p type ZnO produces difficulty, solve the technological problems of MOCVD method growing P-type ZnO film, and then can prepare electricity and inject p-n junction type ZnO photoelectric device.
Technical scheme of the present invention is:
The equipment that p type ZnO film of the present invention growth is used is that described or application number is the special-purpose growth of the described ZnO film of 200410011164.0 a patents MOCVD device systems as No. 02100436.6 patent.The growth technique step of p type ZnO film is as follows.
(1) cleaned substrate is delivered on the substrate slice pallet of reative cell, mechanical pump is opened in the off-response chamber.
(2) reach 10Pa when following when reative cell vacuum degree, can start the turbomolecular pump of reative cell.The vacuum degree of reative cell reaches 3 * 10
-3During Pa, the heated substrate tablet tray is warmed up to 700 ℃ substrate slice was heat-treated 10～30 minutes, and the egative film pallet cools to growth temperature and stops molecular pump for 250～650 ℃, prepares growth.
(3) opened the radio-frequency power supply preheating 10 minutes; High-purity N
2As the mixing chamber of the gas of controlling reative cell air pressure, evenly press down control N again by the high density stainless steel cloth by secondary gas circuit feeding reactor top
2The air pressure that flow is adjusted reative cell is 10
4～10
-1Pa; NO is input to radio-frequency (RF) plasma reactor by the doped source gas circuit with doped source gas, and the NO flow is 10～500sccm, regulates radio-frequency power and reaches build-up of luminance, enters reative cell again after the generation ionization.
(4) open electric rotating machine, regulate the value rotation of substrate slice pallet in 50～1000 rev/mins, regulating the diethyl zinc source temperature is 0 ℃～-25 ℃, regulating Zn source carrier gas Ar throughput is 1～10sccm, feeds reative cell, aerating oxygen, oxygen flow is 10～500sccm, the growth of beginning ZnO film, according to required ZnO film THICKNESS CONTROL growth time, the speed of growth is 0.1～3 μ m/h.
(5) grown after, close all sources of the gas, close radio-frequency (RF) plasma reactor and substrate heater strip, drop to below 200 ℃ after, take out sample.
Effect of the present invention and benefit provide the process that a kind of usefulness is fit to the MOCVD equipment growing P-type ZnO film of suitability for industrialized production, overcome the problem that p type ZnO produces difficulty, solve the technological problems of MOCVD method growing P-type ZnO film, and then can prepare electricity and inject p-n junction type ZnO photoelectric device.
Embodiment
Be described in detail specific embodiments of the invention below in conjunction with technical scheme.
Embodiment 1
(1) substrate clean.Substrate sapphire, Si, GaAs, InP or CaF
2Monocrystalline all can, substrate gets final product with general semi-conductive clean process.
(2) (this step process is applicable to that the application number that the sample pretreatment chamber is housed is the described MOCVD equipment of 200410011164.0 patents to the plasma treatment of substrate.For the described MOCVD equipment of No. 02100436.6 patent that does not have the sample pretreatment chamber, this step process can omit, and cleaned sample substrate directly can be delivered on the substrate slice pallet of reative cell, and the mechanical pump of opening reative cell then vacuumizes).Send cleaned sample substrate to pretreatment chamber, close the door of sample pretreatment chamber.Start mechanical pump the sample pretreatment chamber is vacuumized, treat that the vacuum degree of sample pretreatment chamber reaches 50～10
-1During Pa, by the argon gas of mass flowmenter control feeding 5～50sccm, open the direct current glow discharge plasma generator, Dc bias is adjusted to 300～1000V, and substrate surface is carried out Ar
+Cleaned 5～20 minutes, and closed plasma generator, stop argon gas and feed.The mechanical pump of opening reative cell vacuumizes, and when the vacuum degree of the vacuum degree of reative cell and sample pretreatment chamber is in a basic balance, opens and connects slide valve substrate is sent on the substrate slice pallet of reative cell, closes slide valve.
(3) reach 10Pa when following when reative cell vacuum degree, can start the turbomolecular pump of reative cell.The vacuum degree of reative cell reaches 3 * 10
-3During Pa, the heated substrate tablet tray is warmed up to 700 ℃ substrate slice was heat-treated 10～30 minutes, and the egative film pallet cools to growth temperature and stops molecular pump for 250～650 ℃, prepares growth.
(4) opened the radio-frequency power supply preheating 10 minutes; High-purity N
2As the mixing chamber of the gas of controlling reative cell air pressure, evenly press down control N again by the high density stainless steel cloth by secondary gas circuit feeding reactor top
2The air pressure that flow is adjusted reative cell is 10
4～10
-1Pa; NO is input to radio-frequency (RF) plasma reactor by the doped source gas circuit with doped source gas, and the NO flow is 10～500sccm, and the adjusting radio-frequency power is 100～1000W, reaches build-up of luminance, enters reative cell again after the generation ionization.
(5) open electric rotating machine, regulate the value rotation of substrate slice pallet in 50～1000 rev/mins, regulating the diethyl zinc source temperature is 0 ℃～-25 ℃, regulating Zn source carrier gas Ar throughput is 1～10sccm, feeds reative cell, aerating oxygen, oxygen flow is 10～500sccm, the growth of beginning ZnO film, according to required ZnO film THICKNESS CONTROL growth time, the speed of growth is 0.1～3 μ m/h.
(6) grown after, close all sources of the gas, close radio-frequency (RF) plasma reactor and substrate heater strip, drop to below 200 ℃ after, take out sample.
Embodiment 2
The step of this process and embodiment 1 is identical substantially, institute's difference is to carry out the branch step annealing in the growth course, the concrete practice is, after 250～650 ℃ of growths of growth temperature a period of time (1～20 minute), the zinc source is closed, and thermal anneal process ℃ is carried out in original position heating substrate slice to 700～800, and the processing time is 1～20 minute, the substrate slice temperature is reduced to continued growth again after the growth temperature, repeats such operation and reaches desired thickness until ZnO film.
Embodiment 3
This process is identical with the step of embodiment 1, and institute's difference is that doped source gas adopts N
2O gas; Also can adopt the substep annealing process among the embodiment 2.
Embodiment 4
This process is identical with the step of embodiment 1, and institute's difference is that doped source gas adopts NO and N
2The O mist, the ratio of mixing can be adjusted arbitrarily, i.e. N
2O can be in 0～100% range; Also can adopt the substep annealing process among the embodiment 2.
Embodiment 5
This process is identical with the step of embodiment 1, and institute's difference is that doped source gas adopts NO, N
2O or NO and N
2O mist and O
2Mix feeding, the ratio of mixing is that doped source gas is in 0.1～100% range; Also can adopt the substep annealing process among the embodiment 2.
Claims (4)
1. the Metallorganics chemical vapour deposition (CVD) preparation method of a p type ZnO film is characterized in that, substrate sapphire, Si, GaAs, InP or GaF
2Monocrystalline; Cleaned substrate is delivered on the substrate slice pallet of reative cell, mechanical pump is opened in the off-response chamber; When reative cell vacuum degree reaches 10Pa when following, start the turbomolecular pump of reative cell; The vacuum degree of reative cell reaches 3 * 10
-3During Pa, the heated substrate tablet tray is warmed up to 700 ℃ substrate slice was heat-treated 10～30 minutes, and the egative film pallet cools to growth temperature and stops molecular pump for 250～650 ℃, prepares growth; Opened the radio-frequency power supply preheating 10 minutes; High-purity N
2As the mixing chamber of the gas of controlling reative cell air pressure, evenly press down control N again by the high density stainless steel cloth by secondary gas circuit feeding reactor top
2The air pressure that flow is adjusted reative cell is 10
4～10
-1Pa; NO is input to radio-frequency (RF) plasma reactor by the doped source gas circuit with doped source gas, and the NO flow is 10～500sccm, regulates radio-frequency power and reaches build-up of luminance, enters reative cell again after the generation ionization; Open electric rotating machine, regulate the value rotation of substrate slice pallet in 50～1000 rev/mins, regulating the diethyl zinc source temperature is 0 ℃～-25 ℃, regulating Zn source carrier gas Ar throughput is 1～10sccm, feeds reative cell, aerating oxygen, oxygen flow is 10～500sccm, the growth of beginning ZnO film, according to required ZnO film THICKNESS CONTROL growth time, the speed of growth is 0.1～3 μ m/h; After having grown, close all sources of the gas, close radio-frequency (RF) plasma reactor and substrate heater strip, drop to below 200 ℃ after, take out sample.
2. the Metallorganics chemical vapour deposition (CVD) preparation method of a kind of p type ZnO film according to claim 1, it is characterized in that carrying out in the growth course branch step annealing, the concrete practice is, after 250～650 ℃ of growth temperatures were grown 1～20 minute, the zinc source is closed, and thermal anneal process ℃ is carried out in original position heating substrate slice to 700～800, and the processing time is 1～20 minute, the substrate slice temperature is reduced to continued growth again after the growth temperature, repeats such operation and reaches desired thickness until ZnO film.
3. the Metallorganics chemical vapour deposition (CVD) preparation method of a kind of p type ZnO film according to claim 1 and 2 is characterized in that doped source gas adopts NO and N
2The O mist, the ratio of mixing can be adjusted arbitrarily, i.e. N
2O can be in 0～100% range.
4. the Metallorganics chemical vapour deposition (CVD) preparation method of a kind of p type ZnO film according to claim 1 and 2 is characterized in that doped source gas adopts N
2O, NO or N
2O and NO mist and O
2Mix feeding, the ratio of mixing is that doped source gas is in 0.1～100% range.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100469068A CN100375253C (en) | 2005-07-19 | 2005-07-19 | Metallorganics chemical vapour deposition (CVD) preparing method for p-type ZnO thin film |
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| CNB2005100469068A CN100375253C (en) | 2005-07-19 | 2005-07-19 | Metallorganics chemical vapour deposition (CVD) preparing method for p-type ZnO thin film |
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| CN100375253C true CN100375253C (en) | 2008-03-12 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100494486C (en) * | 2007-05-08 | 2009-06-03 | 中国科学院上海光学精密机械研究所 | Method for developing m-face or a-face ZnO film by metal organic chemical vapour deposition |
| CN100590820C (en) * | 2008-01-13 | 2010-02-17 | 大连理工大学 | Acceptor activation method for nitrogen adulterated ZnO |
| CN101724815B (en) * | 2009-12-16 | 2011-08-17 | 苏州爱迪尔自动化设备有限公司 | Method for preparing energy-saving heating films |
| WO2012037729A1 (en) * | 2010-09-25 | 2012-03-29 | Ye Zhizhen | METHOD FOR MANUFACTURING P-TYPE ZnO-BASED MATERIAL |
| CN102122936A (en) * | 2011-04-08 | 2011-07-13 | 天津理工大学 | Aluminum nitride piezoelectric membrane for surface acoustic wave (SAW) device and preparation method thereof |
| CN102122938A (en) * | 2011-04-08 | 2011-07-13 | 天津理工大学 | Piezoelectric film for high-performance surface acoustic wave (SAW) device and preparation method thereof |
| CN102206856B (en) * | 2011-05-04 | 2012-07-04 | 中国科学院半导体研究所 | Method for growing zinc oxide material by modulating temperature periodically |
| CN103866268B (en) * | 2012-12-11 | 2018-07-13 | 中国科学院微电子研究所 | Donor-acceptor based on nitrogen is co-doped with the preparation method of zinc-oxide film |
| CN106086816A (en) * | 2016-07-06 | 2016-11-09 | 广东振华科技股份有限公司 | A kind of CVD coater |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1377991A (en) * | 2002-01-30 | 2002-11-06 | 吉林大学 | MOCVD equipment and process for growing ZnO film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1377991A (en) * | 2002-01-30 | 2002-11-06 | 吉林大学 | MOCVD equipment and process for growing ZnO film |
Non-Patent Citations (2)
| Title |
|---|
| A comparison of plasma-activated N2/O2 and N2O/O2mixtures for use in ZnO:N synthesis by chemical vapordeposition. Barnes TM, Leaf J, Hand S，et al.JOURNAL OF APPLIED PHYSICS,Vol.96 No.12. 2004 * |
| N doping using N2O and NO sources:From the viewpointofZnO. Matsui H, Saeki H, Kawai T, Tabata H.JOURNAL OF APPLIED PHYSICS,Vol.95 No.10. 2004 * |
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