CN100418192C - Production of iron-doped zinc sulfide growth thin film by growth - Google Patents
Production of iron-doped zinc sulfide growth thin film by growth Download PDFInfo
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- CN100418192C CN100418192C CNB2005100170287A CN200510017028A CN100418192C CN 100418192 C CN100418192 C CN 100418192C CN B2005100170287 A CNB2005100170287 A CN B2005100170287A CN 200510017028 A CN200510017028 A CN 200510017028A CN 100418192 C CN100418192 C CN 100418192C
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Abstract
The invention is concerned with preparing zinc sulfide single-crystal film with iron by low-pressure metal organic chemistry gaseous phase sediment equipment. That is: puts the cleaning semiconductor underlay on the graphite base of the growth room, controls the pressure of the growth room at low, passes over the high-pure hydrogen in the growth room, adjusts high frequency high frequency to heat the graphite base, disposals the underlay 10 minutes -20 minutes at 600 centigrade, uses the cold-trap equipment to control the temperature source of the zinc ethyl and iron pentacarbonyl at the needing value in order to reduces the temperature of the underlay at the best growth temperature, passes over the certain flux hydrogen sulfide (H2S)gas source taking by the high pure hydrogen, iron pentacarbonyl (Fe(CO)5) and zinc dimethyl (DMZn) to the growth room, namely completes the ZnFeS film growth at the condition of low pressure. The invention can get single orientation six-side and four-side ZnFeS single-crystal film with high Fe group.
Description
Technical field:
The invention belongs to technical field of semiconductor, relate to grow a kind of technology of preparing of rare magnetic (half magnetic) semiconductive thin film of low pressure metal organic chemical vapor deposition (MOCVD) equipment.
Background technology:
Optical property and transport property (J.K.Furdyna that dilute magnetic semiconductor (DMS) that magnetic ion mixes or half magnetic semiconductor (SMS) present strong spin correlation, J.Appl.Phys.64, R29 (1988)), for example: strong magneto optical effect (Zeemen effect, faraday rotation etc.), the effective g factor increase in electron hole, negative magnetoresistance effect etc., thereby be to prepare to integrate magnetic, light, electric, the novel semi-conductor electronic device of low-power consumption has been established material and theoretical foundation.One of them landmark progress is exactly recently at ZnMnTe (D.Ferrand, J.Cibert et al, Phys.Rev.B, 63,085201 (2001)) GaMnAs (H.Ohno particularly, Appl.Phys.Lett.69,363 (1996)) ferromagnetic discovery in the system, evoked the new research boom of people, and therefore produced a new subject-semiconductor spintronics, made it be expected to be applied to following self-spining device such as spin fet (S.Datta magnetic semiconductor, B.Das, Appl.Phys.Lett.56,665 (1990)), spin tunneling device (M.Tanaka, Y.Higo, Phys.Rev.Lett.87,026602 (2001)), magnetic random memory and electron spin quantum computer etc.In dilute magnetic semiconductor material research, wide owing to band gap based on the dilute magnetic semiconductor of broadband II-VI family semi-conducting material preparation, exciton bind energy is big, therefore should have bigger magneto optical effect.Thereby application prospect is widely arranged on magnetic-optic devices.As the source that the spin charge carrier is provided, the growing and preparing of magnetic semiconductor material is the most critical link of semiconductor spintronics always.Because the low (H.Ohno of solubility of magnetic impurity in the III-V family semiconductor, Appl.Phys.Lett.69,363 (1996)), even in the concentration of Mn in II I-V family semiconductor under the non-equilibrium crystalline growth condition of low temperature still less than 5%, so this has limited the raising of Curie temperature in this system greatly.But it will not be a problem (J.K.Furdyna that magnetic ion is entrained in the II-VI family semiconductor, J.Appl.Phys.64, R29 (1988)), this is can realize that the magnetic atom of higher concentration mixes because II family magnetic atom of equal value substitutes II family metallic atom, so realize in the II-VI family semiconductor that high-curie temperature has bigger possibility.
The ZnS of transition group ion doping still is considered to promise to be most one of semiconductor of high-curie temperature, thereby has attracted people that the ZnS dilute magnetic semiconductor research that the transition group magnetic ion mixes has been produced great interest.At present, prepare the ZnFeS film both at home and abroad and mostly adopt molecular beam epitaxy (MBE) technology.Though utilize this method can grow all films preferably of crystalline quality and surface topography; but still there is following problem in it: (1) cost height, existing equipment are not popularized, productivity ratio is low, can not drop into large-scale production (2) doping content not high (the mix component of Fe in ZnS is up to 12%).
Summary of the invention
In order to solve in the above-mentioned background technology: existing equipment is not popularized, cost is high, productivity ratio is low, can not drop into large-scale production; Doping content not high (the mix component of Fe in ZnS is up to 12%) the purpose of this invention is to provide the ZnS film growth technology of preparing that Fe mixes.
In order more to be expressly understood the present invention in detail, the ZnS film growth preparation process that Fe mixes is described in detail below:
(a) at first put into the insulation or the semi-insulating substrate of cleaned lattice match on the graphite base in the metal organic chemical vapor deposition growth room, under mechanical pump and low pressure controller effect, growth room's pressure is controlled at 76Torr-200Torr;
(b) utilize the condition of step a, to feed the growth room through the hydrogen of the 6N of palladium tube purifying, and regulate high frequency induction power supply graphite base is heated, and make underlayer temperature rise to 600 ℃ from room temperature, under these conditions to substrate high-temperature process 10 minutes-20 minutes, to remove the substrate surface remaining impurities;
(c) behind the completing steps b, utilize the cold-trap device respectively with zinc methide (DMZn) and iron pentacarbonyl (Fe (CO)
5) temperature source be controlled at required numerical value, and make underlayer temperature reduce to optimum growth temp, growth room's pressure is with step a;
(d) utilize the condition of step c, feed the reaction source hydrogen sulfide (H that carries by high-purity hydrogen
2S) source of the gas, iron pentacarbonyl Fe (CO)
5And zinc methide (DMZn) is to the growth room, wherein above-mentioned reaction source and hydrogen (H
2) flow respectively by the control of mass flowmenter independently; Reaction source epitaxially grown time on insulation that step b handles or semi-insulating substrate is 30-60 minute, can finish the ZnFeS growth for Thin Film under the condition of low pressure.
The difference of the present invention and forefathers' report is that we utilize the MOCVD method to prepare the ZnFeS film, its advantage is: (1) doping content of Fe under growth conditions of the present invention reaches as high as 20%, and can obtain the monocrystal thin films of ZnFeS in this doping content scope, the growth area is at 10 * 10mm
2On the area, the uniformity of its film can reach 98% (non-rotating substrate); (2) the present invention uses MOCVD equipment not only to be suitable for scientific research, and it is more suitable for large-scale production; (3) the selected material system of the present invention is new, yet there are no report with MOCVD method epitaxial growth ZnFeS thin-film material; (4) established material base with the ZnFeS monocrystal thin films of the inventive method preparation for further realizing semiconductor self-spining device, magnetic-optic devices and solar device.Utilize the present invention, at the Al of insulation
2O
3Prepare the ZnFeS film under the different growth pressures on the substrate.The X-ray diffraction measurement result shows sample except the substrate diffraction peak of (0006), has only the diffraction maximum of a growth orientation for the six side ZnFeS films of (0002), shows under our growth conditions, can obtain the ZnFeS monocrystal thin films under above parameter.With the increase of growth pressure, film thickness increases, and the diffraction peak halfwidth increases to some extent, but still is monocrystalline character; The band gap that is shown the ZnFeS monocrystal thin films by absorption spectrum all is a direct band gap between increasing to 20% with the Fe component by 0, and band gap increases with Fe content and diminishes.
Utilize the present invention, at Al
2O
3Prepare the Zn of different Fe content on the substrate
1-XFe
XS film, X-ray diffraction measurement result show have only when the Fe flow when 5ml/min is following, guaranteed that ZnFeS is a monocrystal thin films.
The ZnFeS film that utilizes the present invention to grow on the GaAs substrate show the ZnFeS monocrystal thin films structure that all can obtain its cube in the Fe component is the 1-4ml/min scope by x-ray diffraction pattern, and the component of Fe reaches as high as 18% among the ZnS.
Embodiment:
Embodiment 1:
Under different growth pressures, at the Al of insulation
2O
3Growth ZnFeS film on the substrate.
Adopt low pressure metal organic chemical vapor deposition (MOCVD) equipment of oneself assembling, at first cleaned Al
2O
3Substrate is placed on the graphite base in the metal organic chemical vapor deposition growth room, under mechanical pump and low pressure controller effect growth room's pressure is controlled at low pressure, and it is 0.4MHz that the adjusting high frequency induction power supply makes plasma frequency.When the substrate growth temperature rises to 600 ℃, feed high-purity hydrogen, to substrate processing 10-20 minute by palladium tube purifying 99.9999%.During then with temperature modulation to 350 ℃, feed the hydrogen sulfide H that carries by high-purity hydrogen successively
2S,
Its flow is 10ml/min, iron pentacarbonyl Fe (CO)
5The temperature in source is controlled at 10 ℃, and flow is 1ml/min, and the temperature control of DMZn source is at-27 ℃, and flow is that 8ml/min is to the growth room.Total hydrogen carrier gas is controlled at 2L/min, and the flow-rate ratio of II family hydrogen and VI family hydrogen is 1.2/0.6L/min.Growth time is 40 minutes, and its growth pressure is respectively 76 or 150 or 220Torr.High-frequency induction voltage is 2.6KV.
Utilize the present invention, at the Al of insulation
2O
3Prepare the ZnFeS film under the different growth pressures on the substrate.The X-ray diffraction measurement result shows sample except the substrate diffraction peak of (0006), has only the diffraction maximum of a growth orientation for the six side ZnFeS films of (0002), shows under our growth conditions, can obtain the ZnFeS monocrystal thin films under above parameter.With the increase of growth pressure, film thickness increases, and the diffraction peak halfwidth increases to some extent, but still is monocrystalline character; The band gap that is shown the ZnFeS monocrystal thin films by absorption spectrum all is a direct band gap between increasing to 20% with the Fe component by 0, and band gap increases with Fe content and diminishes.
Embodiment 2:
Under 350 ℃ of the growth temperatures of the best, change Fe (CO)
5Flow growth ZnFeS monocrystal thin films.
Other condition is the same, just changes Fe (CO)
5Flow be 1.5 or 3 or 5ml/min.The ZnFeS that grow this moment is a monocrystal thin films, and ZnFeS is transformed into the polycrystal film structure of six sides and cube mixing by six side's monocrystalline when the Fe flow is 6ml/min.Therefore, have only when the Fe flow when 5ml/min is following, could guarantee that ZnFeS is a monocrystal thin films.
Embodiment 3:
Growth ZnFeS monocrystal thin films on the GaAs substrate.
Adopt (100) GaAs substrate, cleaned GaAs substrate is placed on the graphite base in the metal organic chemical vapor deposition growth room, under mechanical pump and low pressure controller effect, growth room's pressure is controlled at 76Torr, feeding is by the high-purity hydrogen of palladium tube purifying 99.999%, when the substrate growth temperature rises to 600 ℃, substrate processing 10 minutes.Then temperature modulation is arrived 320 ℃ of growth temperatures, feed the hydrogen sulfide H that carries by high-purity hydrogen successively
2S, its flow are 10ml/min, iron pentacarbonyl Fe (CO)
5The temperature in source is controlled at 10 ℃, and flow is 1-4ml/min, and the temperature control of DMZn source is at-27 ℃, and flow is that 8ml/min is to the growth room.Total hydrogen carrier gas is controlled at 2L/min, and the flow-rate ratio of II family hydrogen and VI family hydrogen is 1.2/0.6L/min.Growth time is 40 minutes, and high-frequency induction voltage is 2.6KV.
The ZnFeS film that utilizes the present invention to grow on the GaAs substrate show the ZnFeS monocrystal thin films structure that all can obtain its cube in the Fe component is the 1-4ml/min scope by x-ray diffraction pattern, and the component of Fe reaches as high as 18% among the ZnS.
Claims (1)
1. the zinc sulfide growth thin film by growth preparation method that mixes of iron is characterized in that preparation process is as follows:
(a) at first put into the insulation or the semi-insulating substrate of cleaned lattice match on the graphite base in the metal organic chemical vapor deposition growth room, under mechanical pump and low pressure controller effect, growth room's pressure is controlled at 76Torr-200Torr;
(b) utilize the condition of step a, to feed the growth room through the hydrogen of the 6N of palladium tube purifying, and regulate high frequency induction power supply graphite base is heated, and make underlayer temperature rise to 600 ℃ from room temperature, under these conditions to substrate high-temperature process 10 minutes-20 minutes, to remove the substrate surface remaining impurities;
(c) behind the completing steps b, utilize the cold-trap device temperature source of zinc methide and iron pentacarbonyl to be controlled at-27 ℃ and 10 ℃ respectively, and make underlayer temperature reduce to 350 ℃ or 320 ℃, growth room's pressure is with step a;
(d) utilize the condition of step c, feed the reaction source hydrogen sulfide source of the gas that is carried by 99.9999% high-purity hydrogen, iron pentacarbonyl and zinc methide are to the growth room, and the flow of wherein above-mentioned reaction source and hydrogen is respectively by independently mass flowmenter control; Reaction source epitaxially grown time on insulation that step b handles or semi-insulating substrate is 30-60 minute, can finish the ZnFeS growth for Thin Film under the condition of low pressure.
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| CNB2005100170287A CN100418192C (en) | 2005-08-05 | 2005-08-05 | Production of iron-doped zinc sulfide growth thin film by growth |
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| CNB2005100170287A CN100418192C (en) | 2005-08-05 | 2005-08-05 | Production of iron-doped zinc sulfide growth thin film by growth |
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| CN100418192C true CN100418192C (en) | 2008-09-10 |
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| CN102249288B (en) * | 2011-03-31 | 2013-07-17 | 中国科学院研究生院 | Preparation method for hexagonal phase zinc sulfate nano-crystal coating |
| CN112851351B (en) * | 2020-08-29 | 2021-12-24 | 中国科学院地球化学研究所 | Method for directly synthesizing iron-doped zinc sulfide block through solid-phase reaction |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000264798A (en) * | 1999-03-18 | 2000-09-26 | Sumitomo Electric Ind Ltd | Method for growing ii-vi group compound semiconductor crystal |
| CN1379453A (en) * | 2001-04-12 | 2002-11-13 | 中国科学院长春光学精密机械与物理研究所 | Method suitable for growing zinc sulfide (selenide)-manganese film of broad-band semiconductor |
| US6572705B1 (en) * | 1994-11-28 | 2003-06-03 | Asm America, Inc. | Method and apparatus for growing thin films |
| WO2004020686A2 (en) * | 2002-08-28 | 2004-03-11 | Moxtronics, Inc. | A hybrid beam deposition system and methods for fabricating zno films, p-type zno films, and zno-based ii-vi compound semiconductor devices |
| US20040159854A1 (en) * | 2002-09-20 | 2004-08-19 | Tokyo Institute Of Technology | Thin film device and its fabrication method |
| US6888156B2 (en) * | 2001-06-29 | 2005-05-03 | National Institute For Materials Science | Thin film device |
-
2005
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6572705B1 (en) * | 1994-11-28 | 2003-06-03 | Asm America, Inc. | Method and apparatus for growing thin films |
| JP2000264798A (en) * | 1999-03-18 | 2000-09-26 | Sumitomo Electric Ind Ltd | Method for growing ii-vi group compound semiconductor crystal |
| CN1379453A (en) * | 2001-04-12 | 2002-11-13 | 中国科学院长春光学精密机械与物理研究所 | Method suitable for growing zinc sulfide (selenide)-manganese film of broad-band semiconductor |
| US6888156B2 (en) * | 2001-06-29 | 2005-05-03 | National Institute For Materials Science | Thin film device |
| WO2004020686A2 (en) * | 2002-08-28 | 2004-03-11 | Moxtronics, Inc. | A hybrid beam deposition system and methods for fabricating zno films, p-type zno films, and zno-based ii-vi compound semiconductor devices |
| US20040159854A1 (en) * | 2002-09-20 | 2004-08-19 | Tokyo Institute Of Technology | Thin film device and its fabrication method |
Non-Patent Citations (2)
| Title |
|---|
| Zn1-xCdxS合金薄膜的结构和光学性质. 冯秋菊等.发光学报，第25卷第5期. 2004 * |
| 纳米ZnO薄膜的激子光致发光特性. 肖芝燕等.发光学报，第24卷第4期. 2003 * |
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