CN1293606C - Method or growing N-Al co-blended p type ZnO transistor film by two step method - Google Patents
Method or growing N-Al co-blended p type ZnO transistor film by two step method Download PDFInfo
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- CN1293606C CN1293606C CNB2004100670048A CN200410067004A CN1293606C CN 1293606 C CN1293606 C CN 1293606C CN B2004100670048 A CNB2004100670048 A CN B2004100670048A CN 200410067004 A CN200410067004 A CN 200410067004A CN 1293606 C CN1293606 C CN 1293606C
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- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000013078 crystal Substances 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 239000007789 gas Substances 0.000 claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- 239000010409 thin film Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 5
- 238000004544 sputter deposition Methods 0.000 claims abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000004411 aluminium Substances 0.000 claims abstract description 4
- 239000010408 film Substances 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- 229910052594 sapphire Inorganic materials 0.000 claims description 2
- 239000010980 sapphire Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 2
- 229910000611 Zinc aluminium Inorganic materials 0.000 abstract 1
- 229910045601 alloy Inorganic materials 0.000 abstract 1
- 239000000956 alloy Substances 0.000 abstract 1
- 238000005086 pumping Methods 0.000 abstract 1
- 239000013077 target material Substances 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002800 charge carrier Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000255 optical extinction spectrum Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
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Abstract
The present invention relates to a method for growing a p type ZnO crystal thin film, which adopts a magnetron sputtering method. The vacuum degree of a reaction chamber is at least 4*10<-3>Pa by pumping, zinc aluminium alloy with the aluminium quality content of 0.1 to 0.3% is used as a target material, N2O with the purity of more than 99.99% and O2 with the purity of more than 99.99% are used as sputtering atmosphere, and two gases are respectively controlled by a gas flow counter, are thoroughly mixed by a surge chamber, and are input into a vacuum reaction chamber; the present invention comprises two steps under the pressure of 3 to 5Pa: step 1, a substrate is heated to the temperature of 590 to 610 DEG C under the pressure of 3 to 5Pa, and an N-Al codoping p type ZnO buffer layer thin film is deposited on the substrate; step 2, the substrate temperature is adjusted to 480 to 520 DEG C, and the N-Al codoping p type ZnO crystal thin film grows on a buffer layer. The present invention can realize the real-time codoping of N and Al, the made crystal thin film has good doping evenness, repeatability and stability, good optical performance and p type conduction characteristics.
Description
Technical field
The present invention relates to p type ZnO crystal growth for Thin Film method.
Background technology
Realize of the application of zno-based device, prepare controlled n type and p type ZnO electrically conducting transparent crystal film is its key in all many-sides such as photoelectric fields.At present, people for the research of n type ZnO crystal film relatively fully by donor elements such as doped with Al, Ga, In, F, can realize having the real-time doped growing of the n type ZnO crystal film of excellent properties.Yet the p type of ZnO mixes much more difficult, and this mainly is that acceptor level is generally very dark, and ZnO itself exists many intrinsic alms giver's defectives (as gap zinc Zn because the solid solubility of acceptor doping element in ZnO is very low
iWith room oxygen V
O), to being subjected to the main self compensation effect that can produce height.The real-time doping that how to realize having the p type ZnO film of excellent properties becomes the problem that present urgent need solves.
N is best acceptor doping element, in ZnO, can produce the shallow acceptor energy level, and mixed jointly by main N and active alms giver (as Al, Ga, In) can to improve the solubility of N in ZnO in the ZnO film, obtain more shallow N acceptor level, thereby be a kind of technology that most possibly realizes the good p type conduction of ZnO.At present existing N-Ga, N-In, N-Al mix the report of realizing p type ZnO altogether, but there are some problems in the co-doping p-type film that obtains, the one, the uniformity of crystalline quality and doping is not ideal enough, and the 2nd, the mobility of charge carrier rate is lower, and the 3rd, the repeatability and the stability of the conduction of p type are not high.
Summary of the invention
The objective of the invention is provides a kind of method of two-step method growing N-Al co-blended p type ZnO transistor film for overcoming the above-mentioned problem that exists in the crystal film of mixing altogether.
The method of two-step method growing N-Al co-blended p type ZnO transistor film of the present invention, employing be magnetron sputtering method: put into the reative cell of direct current reaction magnetron sputtering device after will substrate cleaning, reative cell vacuum degree is extracted at least 4 * 10
-3Pa is that 0.1～0.3% allumen is a target with the quality percentage composition of aluminium, with the nitrous oxide (N of purity more than 99.99%
2O) and the O of purity more than 99.99%
2As sputtering atmosphere, with two kinds of gases respectively by the surge chamber of gas flowmeter control input device, fully mix the back at surge chamber and introduce vacuum reaction chamber, under 3～5Pa pressure, the first step, earlier substrate being heated to temperature is 590～610 ℃, carries out the sputter growth, the p type ZnO buffer layer thin film that deposition one deck N-Al mixes altogether on substrate, sedimentation time is 4～6 minutes; Then second step, underlayer temperature is transferred to 480～520 ℃, the p type ZnO crystal film that the N-Al that grows on resilient coating again mixes altogether, growth time is 20～30 minutes.
Among the present invention, O
2As oxygen source, N
2O gas also can be used as oxygen source simultaneously as the nitrogen doped source.Sputter procedure contains sputtered atom and the N of Zn, Al
2O reacts, and generates the ZnO that N-Al mixes altogether.
N
2O gas and O
2Voltage ratio and target in the content of Al regulate according to doping content, the time of growth is by required thickness decision.Said substrate can be silicon or sapphire or quartz or glass.
Advantage of the present invention is:
1) can realize real-time doping, in the ZnO crystal thin film growth process, realize the common doping of N, Al simultaneously;
2) N in content that p type doping content can be by regulating Al in the target and the growth atmosphere
2O: O
2Different dividing potential drops recently control;
3) existence of resilient coating has well improved the crystalline quality of crystal film, makes its orientation of c axle with height;
4) existence of resilient coating has effectively improved mobility of charge carrier rate in the crystal film, makes it have good p type transport properties;
5) existence of resilient coating makes crystal film have uniform doping, repeatability and stable preferably.
Description of drawings
Fig. 1 is the direct current reaction magnetron sputtering device schematic diagram that adopts according to the inventive method.1 and 2 are respectively N among the figure
2O gas and O
2Air inlet pipeline; 3 is flowmeter; 4 is surge chamber; 5 is specimen holder; 6 is heater; 7 is vacuum gauge; 8 is from the dynamic pressure controller; 9 is the S rifle; 10 is baffle plate; 11 is gas introduction tube;
Fig. 2 is x x ray diffraction (XRD) collection of illustrative plates of the p type ZnO crystal film that makes of embodiment;
Fig. 3 is the optical transmission spectrum of the p type ZnO crystal film that makes of embodiment.
Embodiment
Below in conjunction with Fig. 1, the present invention is further illustrated by embodiment.
Earlier substrate will be put on the reative cell specimen holder 5 after cleaning, substrate is desired the deposition table placed face down, effectively prevents granular impurity to the staining of substrate, and reative cell vacuum degree is evacuated to 4 * 10
-3Pa is that 0.15% allumen is a target with the quality percentage composition of aluminium, target is placed on the S rifle 9, with the N of purity more than 99.99%
2O and the O of purity more than 99.99%
2As sputtering atmosphere, two kinds of gases are entered surge chamber 4 through air inlet pipe 1 and 2 respectively, fully mix the back at surge chamber and introduce vacuum reaction chamber by gas introduction tube 11, the pressure in the vacuum chamber is by controlling from dynamic pressure controller 8, and pressure is 4Pa.N
2O and O
2Voltage ratio can be regulated by flowmeter 3 according to the doping needs, and this example is N
2O: O
2=80: 20, under the sputtering power of 54W, begin sputter procedure, the first step is controlled at 600 ℃ with underlayer temperature earlier, the p type ZnO buffer layer thin film that deposition one deck N-Al mixes altogether on substrate, sedimentation time is 5min; Second step was controlled at 500 ℃ with underlayer temperature, the p type ZnO crystal film that the N-Al that grows on resilient coating again mixes altogether, and growth time is 25min.
Be the room temperature electric property of above-mentioned N-Al codoped p type ZnO crystal film shown in the table 1, carrier concentration is 2.47 * 10
17Cm
-3, resistivity 13.5 Ω cm, carrier mobility 1.86cm
2/ V.s shows to have good p type transport properties.
Table 1
| Resistivity (Ω cm) | Carrier mobility (cm 2/V.s) | Carrier concentration (cm -3) | Conduction type |
| 13.5 | 1.86 | +2.47e+17 | p |
X x ray diffraction (XRD) collection of illustrative plates of above-mentioned film is seen Fig. 2, has only (002) diffraction maximum of ZnO to occur, and the halfwidth FWHM at this peak is 0.317 °, shows that the N-Al codoped p type ZnO crystal film that the inventive method makes has good crystal property;
Shown in Figure 3 is the optical transmission spectrum of above-mentioned film.As seen from the figure, about the transmissivity of visible region is up to 90%, a very steep basic absorption limit is arranged at the 390nm place, show that the N-Al codoped p type ZnO crystal film that the inventive method makes has the good optical performance.
Claims (2)
1. the method for two-step method growing N-Al co-blended p type ZnO transistor film is characterized in that: put into the reative cell of direct current reaction magnetron sputtering device after will substrate cleaning, reative cell vacuum degree is extracted at least 4 * 10
-3Pa is that 0.1～0.3% allumen is a target with the quality percentage composition of aluminium, with the N of purity more than 99.99%
2O and the O of purity more than 99.99%
2As sputtering atmosphere, with two kinds of gases respectively by the surge chamber of gas flowmeter control input device, fully mix the back at surge chamber and introduce vacuum reaction chamber, under 3～5Pa pressure, the first step, earlier substrate being heated to temperature is 590～610 ℃, carries out the sputter growth, the p type ZnO buffer layer thin film that deposition one deck N-Al mixes altogether on substrate, sedimentation time is 4～6 minutes; Then second step, underlayer temperature is transferred to 480～520 ℃, the p type ZnO crystal film that the N-Al that grows on resilient coating again mixes altogether, growth time is 20～30 minutes.
2. the method for two-step method growing N-Al co-blended p type ZnO transistor film according to claim 1 is characterized in that said substrate is silicon or sapphire or quartz or glass.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100670048A CN1293606C (en) | 2004-09-30 | 2004-09-30 | Method or growing N-Al co-blended p type ZnO transistor film by two step method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100670048A CN1293606C (en) | 2004-09-30 | 2004-09-30 | Method or growing N-Al co-blended p type ZnO transistor film by two step method |
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| Publication Number | Publication Date |
|---|---|
| CN1588623A CN1588623A (en) | 2005-03-02 |
| CN1293606C true CN1293606C (en) | 2007-01-03 |
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| CNB2004100670048A Expired - Fee Related CN1293606C (en) | 2004-09-30 | 2004-09-30 | Method or growing N-Al co-blended p type ZnO transistor film by two step method |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317749C (en) * | 2005-04-05 | 2007-05-23 | 中国科学院物理研究所 | Three-dopant contained P-type zinc oxide film and method for making same |
| US7927713B2 (en) * | 2007-04-27 | 2011-04-19 | Applied Materials, Inc. | Thin film semiconductor material produced through reactive sputtering of zinc target using nitrogen gases |
| JP5718052B2 (en) | 2007-08-02 | 2015-05-13 | アプライド マテリアルズ インコーポレイテッドＡｐｐｌｉｅｄ Ｍａｔｅｒｉａｌｓ，Ｉｎｃｏｒｐｏｒａｔｅｄ | Thin film transistor using thin film semiconductor material |
| US8980066B2 (en) | 2008-03-14 | 2015-03-17 | Applied Materials, Inc. | Thin film metal oxynitride semiconductors |
| WO2009117438A2 (en) | 2008-03-20 | 2009-09-24 | Applied Materials, Inc. | Process to make metal oxide thin film transistor array with etch stopping layer |
| US8258511B2 (en) | 2008-07-02 | 2012-09-04 | Applied Materials, Inc. | Thin film transistors using multiple active channel layers |
| JP5889791B2 (en) | 2009-09-24 | 2016-03-22 | アプライド マテリアルズ インコーポレイテッドＡｐｐｌｉｅｄ Ｍａｔｅｒｉａｌｓ，Ｉｎｃｏｒｐｏｒａｔｅｄ | Method of manufacturing metal oxide or metal oxynitride TFT using wet process for source / drain metal etching |
| US8840763B2 (en) | 2009-09-28 | 2014-09-23 | Applied Materials, Inc. | Methods for stable process in a reactive sputtering process using zinc or doped zinc target |
| CN103305792A (en) * | 2012-03-14 | 2013-09-18 | 江苏新源动力有限公司 | Zinc-oxide-doped transparent film and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001068707A (en) * | 1999-08-27 | 2001-03-16 | Univ Osaka | Conductive material, manufacture thereof, conductive thin-film, and composite film |
| US6291085B1 (en) * | 1998-08-03 | 2001-09-18 | The Curators Of The University Of Missouri | Zinc oxide films containing P-type dopant and process for preparing same |
| CN1391259A (en) * | 2002-07-17 | 2003-01-15 | 浙江大学 | Process for growing P-type ZnO crystal film by real-time doping nitrogen |
| CN1440053A (en) * | 2003-03-25 | 2003-09-03 | 浙江大学 | P-ZnO thin film and preparation thereof |
-
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- 2004-09-30 CN CNB2004100670048A patent/CN1293606C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6291085B1 (en) * | 1998-08-03 | 2001-09-18 | The Curators Of The University Of Missouri | Zinc oxide films containing P-type dopant and process for preparing same |
| JP2001068707A (en) * | 1999-08-27 | 2001-03-16 | Univ Osaka | Conductive material, manufacture thereof, conductive thin-film, and composite film |
| CN1391259A (en) * | 2002-07-17 | 2003-01-15 | 浙江大学 | Process for growing P-type ZnO crystal film by real-time doping nitrogen |
| CN1440053A (en) * | 2003-03-25 | 2003-09-03 | 浙江大学 | P-ZnO thin film and preparation thereof |
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