CN1787246A - UV electroluminescence device of silicon base zinc oxide and preparation process thereof - Google Patents
UV electroluminescence device of silicon base zinc oxide and preparation process thereof Download PDFInfo
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- CN1787246A CN1787246A CNA2005100616033A CN200510061603A CN1787246A CN 1787246 A CN1787246 A CN 1787246A CN A2005100616033 A CNA2005100616033 A CN A2005100616033A CN 200510061603 A CN200510061603 A CN 200510061603A CN 1787246 A CN1787246 A CN 1787246A
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- zno
- zno film
- silicon substrate
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 53
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 37
- 239000010703 silicon Substances 0.000 title claims abstract description 37
- 238000005401 electroluminescence Methods 0.000 title claims description 15
- 238000002360 preparation method Methods 0.000 title claims description 7
- 238000004544 sputter deposition Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 238000000151 deposition Methods 0.000 claims abstract description 9
- 239000011701 zinc Substances 0.000 claims abstract description 6
- 230000008021 deposition Effects 0.000 claims abstract description 5
- 238000003980 solgel method Methods 0.000 claims abstract description 4
- 238000001704 evaporation Methods 0.000 claims abstract description 3
- 230000008020 evaporation Effects 0.000 claims abstract description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 5
- 238000005229 chemical vapour deposition Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 6
- 229910052681 coesite Inorganic materials 0.000 abstract 3
- 229910052906 cristobalite Inorganic materials 0.000 abstract 3
- 239000000377 silicon dioxide Substances 0.000 abstract 3
- 235000012239 silicon dioxide Nutrition 0.000 abstract 3
- 229910052682 stishovite Inorganic materials 0.000 abstract 3
- 229910052905 tridymite Inorganic materials 0.000 abstract 3
- 239000013077 target material Substances 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 239000003595 mist Substances 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000001451 molecular beam epitaxy Methods 0.000 description 2
- 229910002704 AlGaN Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001194 electroluminescence spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000001552 radio frequency sputter deposition Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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Abstract
The invention discloses a silicon-base zinc oxide UV electroluminescent device and the preparing method thereof. The device is in turn deposited with ZnO film, SiO2 film and electrode on a silicon substrate from the bottom up, and deposited with ohm contact electrode in the back of the silicon substrate. And the preparing steps as follows: firstly washing a N-type silicon wafer and putting the wafer into the reaction chamber of a DC reaction magnetic-controlled sputtering device, vacuumizing the reaction chamber, using Zn as target material and using O2 and Ar as sputtering atmosphere to make sputtering growth and obtaining the ZnO film; then using chemical gas phase deposition or evaporation or sputtering or sol-gel method to deposit the SiO2 film on the ZnO film; sputtering the electrode on the SiO2 film and the ohm contact electrode in the back of the silicon substrate. The device has simple structure and implementing mode, and need not adopt a p-type ZnO film, thus avoiding the difficulty of p-type doping of the ZnO film. And the equipment that the preparing method uses is compatible with that of the existing mature silicon device plane process.
Description
Technical field
The present invention relates to UV electroluminescence device of silicon base zinc oxide and preparation method thereof.
Background technology
Because ZnO at room temperature has the exciton bind energy of direct band gap and the 60mev of 3.37eV, so it is a desirable photoelectron material of realizing ultra-violet light-emitting.But the electricity of ZnO causes ultraviolet light-emitting diode and laser diode is difficult to realize, the biggest obstacle that it runs into is that the P type doping of ZnO high concentration exists suitable difficulty.In order to avoid this difficulty, people had once attempted the electroluminescence of multiple heterojunction structure with the realization zno-based, as: n-ZnO/p-GaN, p-AlGaN/n-ZnO and p-SrCu
2O
2/ n-ZnO, the report document has: Ya.I.Alivov, J.E.Van Nostrand, D.C-Look, M.V Chukichev, and B.M.Ataev, Appl.Phys.Lett.83,2943 (2003); Ya.I.Alivov, E.V.Kalinina, A.E.Cherenkov, D.C.Look, B.M.Ataev, A.K.Omaev, M.V.Chukichev, D.M.Bagnall, Appl.Phys.Lett.83,4719 (2003); H.Ohta, M.Orita, and M.Hirano, and H.Hosono, J.Appl.Phys.89,5720 (2001).At the homogeneity LED aspect of ZnO, people such as Toru Aoki have reported with laser doping and have realized the ZnO diode, and obtained ultra-violet light-emitting (list of references T.Aoki under 110K, Y.Hatanaka, and D.C.Look, Appl.Phys.Lett.76,3257 (2000)); People such as Xin-Li Guo utilize N
2O plasma intensifier pulse laser reactive sedimentation has realized that the P type of ZnO mixes, thereby obtains the ZnO light-emitting diode, but at luminous very faint (the list of references X.L.Guo of ultraviolet region, J.H.Choi, H.Tabata, and T.Kawai, Jpn.J.Appl.Phys.40, L177 (2001)); People such as Atsushi Tsukazaki have reported that repeated temperature modulation epitaxy realizes that the P type mixes, thereby prepared the ZnO diode, and obtained electroluminescence from ultraviolet to the green glow zone, yet luminous still more weak (list of references A.Tsukazaki, A.Ohtomo, the T.Onuma of ultraviolet region, M.Ohtani, T.Makino, M.Sumiya, K.Ohtani, S.F.Chichibu, S.Fuke, Y.Segawa, H.Ohno, H.Koinuma, and M.Kawasaki, NatureMater.4,42 (2005)).Under but the practicability P of ZnO type mixes the situation that does not also have at present thoroughly to solve, adopt MIS structure to remain the electroluminescent approach of ZnO that realizes based on ZnO.In fact, just reported the ultra-violet light-emitting of Ag/SiO/ZnO and Au/SiO/ZnO structure in the 1970's, should be noted that, what adopt in these structures is the ZnO monocrystal, and luminous (the list of references B.W.Thomas and D.Walsh that under high bias voltage (tens volts even 200V), produces, Electron.Lett.9,362 (1973); T.Minami, M.Tanigawa, M.Yamanishi, and T.Kawamura, Jpn.J.Appl.Phys.13,1475 (1974)).Recently, people such as Ya.I.Alivov utilizes the nitrogen ion to be infused in Al
2O
3Form insulating barrier in the base n type ZnO film, thereby form zno-based MIS structure and obtained ultra-violet light-emitting (list of references Ya.I.Alivov, D.C.Look, B.M.Ataev, M.V.Chukichev, V.V.Mamedov, V.I.Zinenko, Yu.A.Agafonov, and A.N.Pustovit, Solid-State Electron.48,2343 (2004)).Up to the present, some progress have been obtained though cause the exploitation of ultra-violet light-emitting device based on the electricity of ZnO, but all adopted comparatively complicated implementation method, such as: prepare P type compound semiconductor film with molecular beam epitaxy (MBE) and metal-organic chemical vapor deposition equipment (MOCVD) method.
Summary of the invention
The objective of the invention is to propose a kind of simple UV electroluminescence device of silicon base zinc oxide and preparation method thereof.
UV electroluminescence device of silicon base zinc oxide of the present invention is characterized in that depositing ZnO film, SiO from bottom to top successively in the front of silicon substrate
2Film and electrode have Ohm contact electrode at the silicon substrate backside deposition.
The preparation method of the UV electroluminescence device of silicon base zinc oxide of invention may further comprise the steps:
1) be 0.005-50 ohm with resistivity. centimetre N type silicon chip put into the reative cell of direct current reaction magnetron sputtering device after cleaning, reative cell vacuum degree is evacuated to 1~5 * 10
-3Pa is a target with Zn, with O
2With Ar as sputtering atmosphere, O
2With the flow-rate ratio of Ar be O
2: Ar=1: 2~1: 5, under 10~20Pa pressure, underlayer temperature is 300 ℃~600 ℃, carries out the sputter growth, obtains ZnO film;
2) utilize conventional chemical vapour deposition technique or evaporation or sputtering method or sol-gel process on ZnO film, to deposit SiO
2Film;
3) at SiO
2Sputter semitransparent electrode on the film is at N type silicon substrate back spatter Ohm contact electrode.
Above-mentioned semitransparent electrode can be the thick golden film of ito thin film or 2-10nm.
The present invention can change the crystalline state of ZnO film by the adjusting underlayer temperature, by adjusting the thickness that sputtering time changes ZnO film.
Beneficial effect of the present invention is: the structure and the implementation of device are simple, do not need to adopt complicated molecular beam epitaxy (MBE) and metal-organic chemical vapor deposition equipment means such as (MOCVD).This device need not to adopt P type ZnO film, thereby has avoided the problem of ZnO film P type doping difficulty.In addition, used equipment and the existing mature silicon device plane process compatibility of this preparation of devices method.
Description of drawings
Fig. 1 is the UV electroluminescence device of silicon base zinc oxide schematic diagram;
Fig. 2 is the electroluminescence spectrum that UV electroluminescence device of silicon base zinc oxide obtains under different forward bias.
Embodiment
Further specify the present invention below in conjunction with accompanying drawing.
With reference to Fig. 1, the UV electroluminescence device of silicon base zinc oxide of invention deposits ZnO film 2, SiO from bottom to top successively in the front of silicon substrate 1
2 Film 3 and electrode 4 have Ohm contact electrode 5 at the silicon substrate backside deposition.
Take following processing step: 1) clean N type<100 〉, resistivity is 0.005 ohm. centimetre, size is 15 * 15mm
2, thickness is 675 microns silicon chip, puts into the reative cell of direct current reaction magnetron sputtering device after the cleaning, reative cell vacuum degree is evacuated to 1 * 10
-3Pa; On silicon chip, utilize the method deposit thickness that reacts direct current sputtering to be about the ZnO film of 300nm, when sputter, adopt Zn target, 300 ℃ of underlayer temperatures, sputtering power 120W, pass to O
2With Ar mist, O
2With the flow-rate ratio of Ar be 1: 2, operating pressure is 10Pa; 2) adopting mol ratio is positive tetraethyl orthosilicate (TEOS): ethanol (EtOH): H
2O=1: 10: 10 precursor solution, and add an amount of HCl as catalyst, utilize sol-gel process spin-on deposition thickness on ZnO film to be about the SiO of 200nm
2Film, after the spin coating 80 ℃ of down oven dry 20 minutes, then 650 ℃ of heat treatments 2 hours under oxygen; 3) at SiO
2On the film and the silicon substrate back side is sputter 10nm and the thick Au film of 100nm, wherein the former area 10 * 10mm respectively
2
Take following processing step: 1) clean N type<100 〉, resistivity is 0.5 ohm. centimetre, size is 15 * 15mm
2, thickness is 675 microns silicon chip, puts into the reative cell of direct current reaction magnetron sputtering device after the cleaning, reative cell vacuum degree is evacuated to 5 * 10
-3Pa; On silicon chip, utilize the method deposit thickness that reacts direct current sputtering to be about the ZnO film of 300nm, when sputter, adopt Zn target, 500 ℃ of underlayer temperatures, sputtering power 120W, pass to O
2With Ar mist, O
2With the flow-rate ratio of Ar be 1: 3, operating pressure is 20Pa, 2) with SiO
2Be target, utilize RF sputtering method deposit thickness on ZnO film to be about the SiO of 100nm
2Film, sputtering power are 100W, and working gas is an argon gas, and operating pressure is 10Pa; 3) at SiO
2The thick ito thin film of sputtering sedimentation 50nm on the film is at the thick Au film of silicon substrate back spatter 100nm, wherein the former area 10 * 10mm
2
Take following processing step: 1) clean N type<100 〉, resistivity is 50 ohm. centimetre, size is 15 * 15mm
2, thickness is 675 microns silicon chip, puts into the reative cell of direct current reaction magnetron sputtering device after the cleaning, reative cell vacuum degree is evacuated to 3 * 10
-3Pa; On silicon chip, utilize the method deposit thickness that reacts direct current sputtering to be about the ZnO film of 300nm, when sputter, adopt Zn target, 500 ℃ of underlayer temperatures, sputtering power 120W, pass to O
2With Ar mist, O
2With the flow-rate ratio of Ar be 1: 3, operating pressure is 20Pa; 2) be source of the gas with positive tetraethyl orthosilicate (TEOS), utilize chemical gaseous phase depositing process deposit thickness on ZnO film to be about the SiO of 100nm
2Film, depositing temperature are 500 ℃, and operating pressure is 100Torr; 3) at SiO
2The thick ito thin film of sputtering sedimentation 50nm on the film is at the thick Au film of silicon substrate back spatter 100nm, wherein the former area 10 * 10mm
2
Fig. 2 has provided the different driving voltage/current electroluminescence (EL) down that the device that obtains by said method at room temperature records and has composed, and during forward bias, negative pressure is added on the silicon substrate.As can be seen from the figure, along with the increase of current/voltage, electroluminescent intensity is also along with increase, and this is typical electroluminescent feature.In addition, the position of glow peak is near 388nm, and this derives from the ultraviolet light emission that the nearly band edge transition of ZnO produces.
Claims (2)
1. UV electroluminescence device of silicon base zinc oxide is characterized in that depositing ZnO film (2), SiO from bottom to top successively in the front of silicon substrate (1)
2Film (3) and electrode (4) have Ohm contact electrode (5) at the silicon substrate backside deposition.
2. the preparation method of UV electroluminescence device of silicon base zinc oxide according to claim 1 is characterized in that may further comprise the steps:
1) be 0.005-50 ohm with resistivity. centimetre N type silicon chip put into the reative cell of direct current reaction magnetron sputtering device after cleaning, reative cell vacuum degree is evacuated to 1~5 * 10
-3Pa is a target with Zn, with O
2With Ar as sputtering atmosphere, O
2With the flow-rate ratio of Ar be O
2: Ar=1: 2~1: 5, under 10~20Pa pressure, underlayer temperature is 300 ℃~600 ℃, carries out the sputter growth, obtains ZnO film;
2) utilize chemical vapour deposition technique or evaporation or sputtering method or sol-gel process on ZnO film, to deposit SiO
2Film;
3) at SiO
2Sputter semitransparent electrode on the film is at N type silicon substrate back spatter Ohm contact electrode.
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JPH05114482A (en) * | 1991-10-22 | 1993-05-07 | Toyota Motor Corp | Manufacture of transmission type electroluminescent element |
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CN1246508C (en) * | 2003-11-04 | 2006-03-22 | 浙江大学 | Metal organic compound vapor deposition device for the growth of zinc oxide semiconductor film |
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CN100413114C (en) * | 2006-09-30 | 2008-08-20 | 浙江大学 | Zinc oxide negative resistance device and producing method thereof |
CN100449810C (en) * | 2006-12-30 | 2009-01-07 | 浙江大学 | Silicon based MgxZn1-xO ultraviolet electroluminescent device and method for producing the same |
CN102040187A (en) * | 2010-11-12 | 2011-05-04 | 浙江大学 | Method for growing core-shell structure ZnO nanowire array |
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CN102931583B (en) * | 2012-11-26 | 2014-06-25 | 浙江大学 | Electrically pumped random laser device based on dual SiO2-ZnO structure and preparation method and application thereof |
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