CN1601710A - Method of growing N-Al Co-doped p-type ZnO crystal membrane under protection of Ar - Google Patents
Method of growing N-Al Co-doped p-type ZnO crystal membrane under protection of Ar Download PDFInfo
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- CN1601710A CN1601710A CN 200410067001 CN200410067001A CN1601710A CN 1601710 A CN1601710 A CN 1601710A CN 200410067001 CN200410067001 CN 200410067001 CN 200410067001 A CN200410067001 A CN 200410067001A CN 1601710 A CN1601710 A CN 1601710A
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- 239000013078 crystal Substances 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000012528 membrane Substances 0.000 title 1
- 239000007789 gas Substances 0.000 claims abstract description 26
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000004544 sputter deposition Methods 0.000 claims abstract description 6
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 238000004140 cleaning 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
- 238000004062 sedimentation Methods 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
- 230000003287 optical effect Effects 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000013077 target material Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 29
- 239000011701 zinc Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000010409 thin film 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002800 charge carrier Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000255 optical extinction spectrum Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000001681 protective effect Effects 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
- 230000001133 acceleration Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 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
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
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Abstract
Magnetron sputtering method is adopted in the disclosed method. vacuum degree in the reaction chamber is pumped to 4X10-3Pa. Allumen is as target material. N2O in purity 99.99% and Ar in purity 99.99% are as sputtering atmospheres. Under control of gas flow meter, two kinds of gases are input to buffer chamber, where gases are mixed and input to vacuum reaction chamber. Under condition of 3-5Pa intensity of pressure and substrate at temp 450-550 deg.C, sputtering growth is carried out so as to deposit the said ZnO crystal film on substrate. Advantages are: better evenness of adulteration, repeatability and stability, favorable optical property 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 the application of zno-based device, prepare controlled n type and p type ZnO electrically conducting transparent crystal film is necessary.At present, people are relatively more abundant for the research of n type ZnO crystal film, by doped with II I valency element, can realize real-time, the controlled n type ZnO crystal growth for Thin Film of concentration, have excellent performance.Yet because the solid solubility of ZnO acceptor doping element in ZnO be very low, acceptor level is generally very dark, and the hole is not easy to thermal excitation and enters valence band, and there are many intrinsic alms giver's defectives in ZnO itself, as gap zinc Zn
iWith room oxygen V
O, give birth to the height auto-compensation to being subjected to main product, these factors are mixed the p type of ZnO and are become difficult unusually, become the bottleneck of restriction ZnO Application and Development.
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 the method for growing N-Al co-blended p type ZnO transistor film under a kind of Ar gas shiled for overcoming the above-mentioned problem that exists in the crystal film of mixing altogether.
The method of growing N-Al co-blended p type ZnO transistor film under the Ar gas shiled 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, heated substrate, underlayer temperature is controlled at 450～550 ℃, is target with the allumen, and wherein the quality percentage composition of aluminium is 0.1～0.3%, with the nitrous oxide (N of purity more than 99.99%
2O) and the Ar gas of purity more than 99.99% as 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, the gas total pressure is 3～5Pa, the dividing potential drop of Ar is adjusted into 15～25% of gas total pressure, carry out the sputter growth, the p type ZnO crystal film that deposition N-Al mixes altogether on substrate, sedimentation time is 20～40min.
Among the present invention, N
2O gas is both as oxygen source, again as the nitrogen doped source.Sputter procedure, the sputtered atom that contains Zn, Al under the protective effect of Ar gas with N
2O reacts, and generates the p type ZnO crystal film that N-Al mixes altogether.In sputter procedure, Ar gas plays a very good protection to the generation of N-Al co-doping p-type ZnO crystal film, on the one hand, promotes N
2The sputter of the decomposition of O and Zn, Al atom, sputtered atom and the N of acceleration Zn, Al
2The reaction of O is improved the p type transport properties of ZnO crystal film; On the other hand, utilize the bombardment effect of Ar atom pair film, can improve the evenness of crystal film, avoid the deposition of pollutant on film simultaneously, thereby improve the crystalline quality of crystal film.
N
2The content of Al is regulated according to doping content in the voltage ratio of O gas and Ar and the target, and 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
2The different dividing potential drops of O: Ar are recently controlled;
3) utilize the protective effect of Ar gas, well improved the crystalline quality of N-Al co-doping p-type ZnO film, reduced the surface roughness of film;
4) effectively improved mobility of charge carrier rate in the N-Al co-doping p-type ZnO film, made above-mentioned film have good p type transport properties;
5) N-Al co-doping p-type ZnO film has 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 example.
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 Ar of purity more than 99.99% are as 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 Ar voltage ratio can be regulated by flowmeter 3 according to the doping needs, and the dividing potential drop of this routine Ar is 20% of a gas total pressure, begins sputter procedure under the sputtering power of 54W, generates the p type ZnO crystal film that N-Al mixes altogether on substrate, and growth time is 30min.
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 4.45 * 10
17Cm
-3, resistivity 7.58 Ω cm, carrier mobility 1.84cm
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
7.58 1.84 4.45e+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 0.306 °, 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.Ar the method for growing N-Al co-blended p type ZnO transistor film under the gas shiled is characterized in that: will put into the reative cell of direct current reaction magnetron sputtering device after the 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 Ar of purity more than 99.99% are as sputtering atmosphere, the dividing potential drop of Ar is 15～25% of a gas total pressure, 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, it is 450～550 ℃ that substrate is heated to temperature, carries out the sputter growth, the p type ZnO crystal film that deposition N-Al mixes altogether on substrate, sedimentation time is 20～40min.
2. the method for growing N-Al co-blended p type ZnO transistor film under the Ar gas shiled according to claim 1 is characterized in that said substrate is silicon or sapphire or quartz or glass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410067001 CN1601710A (en) | 2004-09-30 | 2004-09-30 | Method of growing N-Al Co-doped p-type ZnO crystal membrane under protection of Ar |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410067001 CN1601710A (en) | 2004-09-30 | 2004-09-30 | Method of growing N-Al Co-doped p-type ZnO crystal membrane under protection of Ar |
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| Publication Number | Publication Date |
|---|---|
| CN1601710A true CN1601710A (en) | 2005-03-30 |
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| CN 200410067001 Pending CN1601710A (en) | 2004-09-30 | 2004-09-30 | Method of growing N-Al Co-doped p-type ZnO crystal membrane under protection of Ar |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101671842B (en) * | 2009-10-26 | 2011-07-20 | 浙江大学 | Method for growing Na-N co-doping p-type ZnO crystal film by annealing |
| WO2012001542A1 (en) | 2010-07-02 | 2012-01-05 | Centre National De La Recherche Scientifique | P-type doped zinc oxide |
| CN103103479A (en) * | 2013-01-31 | 2013-05-15 | 浙江大学 | Method for preparing p-type zinc oxide film through sulfur and nitrogen co-doping |
-
2004
- 2004-09-30 CN CN 200410067001 patent/CN1601710A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101671842B (en) * | 2009-10-26 | 2011-07-20 | 浙江大学 | Method for growing Na-N co-doping p-type ZnO crystal film by annealing |
| WO2012001542A1 (en) | 2010-07-02 | 2012-01-05 | Centre National De La Recherche Scientifique | P-type doped zinc oxide |
| CN103103479A (en) * | 2013-01-31 | 2013-05-15 | 浙江大学 | Method for preparing p-type zinc oxide film through sulfur and nitrogen co-doping |
| CN103103479B (en) * | 2013-01-31 | 2015-06-24 | 浙江大学 | Method for preparing p-type zinc oxide film through sulfur and nitrogen co-doping |
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