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WO2003034510A1 - Film mince en oxyde de zinc de type p, compose semiconducteur dote de ce film, et procede de fabrication correspondant - Google Patents

Film mince en oxyde de zinc de type p, compose semiconducteur dote de ce film, et procede de fabrication correspondant Download PDF

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Publication number
WO2003034510A1
WO2003034510A1 PCT/KR2002/001952 KR0201952W WO03034510A1 WO 2003034510 A1 WO2003034510 A1 WO 2003034510A1 KR 0201952 W KR0201952 W KR 0201952W WO 03034510 A1 WO03034510 A1 WO 03034510A1
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WO
WIPO (PCT)
Prior art keywords
zinc oxide
thin film
oxide thin
type
type dopant
Prior art date
Application number
PCT/KR2002/001952
Other languages
English (en)
Inventor
Jae-Min Myoung
Original Assignee
Bluetron Inc.
Lim, Yong-Jin
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bluetron Inc., Lim, Yong-Jin filed Critical Bluetron Inc.
Publication of WO2003034510A1 publication Critical patent/WO2003034510A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S5/00—Semiconductor lasers
    • H01S5/30—Structure or shape of the active region; Materials used for the active region
    • H01S5/32—Structure or shape of the active region; Materials used for the active region comprising PN junctions, e.g. hetero- or double- heterostructures
    • H01S5/323—Structure or shape of the active region; Materials used for the active region comprising PN junctions, e.g. hetero- or double- heterostructures in AIIIBV compounds, e.g. AlGaAs-laser, InP-based laser
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/81—Bodies
    • H10H20/822—Materials of the light-emitting regions
    • H10H20/823—Materials of the light-emitting regions comprising only Group II-VI materials, e.g. ZnO
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S5/00—Semiconductor lasers
    • H01S5/30—Structure or shape of the active region; Materials used for the active region
    • H01S5/32—Structure or shape of the active region; Materials used for the active region comprising PN junctions, e.g. hetero- or double- heterostructures
    • H01S5/327—Structure or shape of the active region; Materials used for the active region comprising PN junctions, e.g. hetero- or double- heterostructures in AIIBVI compounds, e.g. ZnCdSe-laser
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S2304/00—Special growth methods for semiconductor lasers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S5/00—Semiconductor lasers
    • H01S5/30—Structure or shape of the active region; Materials used for the active region
    • H01S5/305—Structure or shape of the active region; Materials used for the active region characterised by the doping materials used in the laser structure
    • H01S5/3054—Structure or shape of the active region; Materials used for the active region characterised by the doping materials used in the laser structure p-doping
    • H01S5/3059—Structure or shape of the active region; Materials used for the active region characterised by the doping materials used in the laser structure p-doping in II-VI materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/81—Bodies
    • H10H20/822—Materials of the light-emitting regions
    • H10H20/824—Materials of the light-emitting regions comprising only Group III-V materials, e.g. GaP
    • H10H20/8242—Materials of the light-emitting regions comprising only Group III-V materials, e.g. GaP characterised by the dopants

Definitions

  • the present invention relates to a p-type zinc oxide thin film, an optoelectronic power compound semiconductor using the same, and a manufacturing method thereof, and more particularly, to a p-type zinc oxide thin film having a hole concentration higher than 10 19 /cm 3 produced, in which a p-type dopant, Group N element of As and an n-type dopant, Group III element of Ga are dual-doped to control the concentration of the two elements appropriately.
  • the present invention is directed to a- manufacturing method of a zinc oxide thin film having a hole concentration higher than 10 19 /cm 3 produced by depositing a zinc oxide thin film to a predetermined thickness on a substrate made of the elements to be doped and thermally annealing the resulting substrate so that a doping material is dual-doped into the zinc oxide thin film to a predetermined concentration.
  • zinc oxide is a material that many studies are being made for the past several decades because of its good electrical, optical and piezoelectric characteristics, and has a high possibility to be useful in a surface acoustic device, a transparent electrode, and an optical device, etc.
  • the zinc oxide has a characteristic of a wide band gap of 3.37 eV, and may change the band gap as high as 4 eV by addition of Mg or the like. Accordingly, the zinc oxide is regarded as a material of an optical device for next generation, being capable of oscillating a laser corresponding to the frequency range of ultraviolet rays .
  • the development of a quantum well structure by minimization of nanometer unit is known to greatly improve the optical characteristics.
  • the optical device for a Group D nitride compound such as GaN is now in a step of practical uses.
  • most of the nitride compounds, which GaN is representative of require a high temperature higher than 1000 °C during a growing step of a thin film, so that limitation still remains in selecting an appropriate substrate, and therefore, it is found that the growth of a high quality of an epitaxial thin film in the Si-substrate which is used most availably in manufacturing processes is difficult.
  • a zinc oxide semiconductor has a 60 meV of exciton binding energy at a room temperature which is much greater compared with the case of 28 meV of GaN to maximize the efficiency of an optical device operatable at a room temperature and a high temperature.
  • the zinc oxide can be used to grow a high quality of an epitaxial thin film even at a comparably low temperature of about 500 °C, it is found to be possible and easy to grow an epitaxial film on a Si-substrate compared with the case of GaN, and therefore, the zinc oxide is much more advantageous for practical uses. Owing to advantages of the material characteristic, many experiments have been made to produce a high quality of a zinc oxide epitaxial thin film since 1990s.
  • the applications in optical devices such as laser, etc. require a high quality material of single crystal, but zinc oxide has characteristics of difficulty in being manufactured as single crystal in bulk type up to now, and so, it should be necessarily subject to a hetero epitaxial growth process.
  • lattice constant difference between most of substrate materials solder (A1 2 0 3 ) , Si) and a grown film is great, the grown thin film has many defects, which seriously affect optical property, etc. Accordingly, it is required that the lattice constant difference should be minimized.
  • the zinc oxide thin film generally shows an n-type electric conductivity by Zn interstitial atoms or 0 2 vacancies, which causes a serious problem in a p-type doping.
  • An ultraviolet rays detecting device is used for military usages like guidance systems of missile and rocket, etc., industrial usages like ultraviolet rays detecting in frame, air environment research, and engine monitoring, etc., research usages of plasma examination, etc., and academic usages of astronomy, etc.
  • the ultraviolet rays detecting device is expected to be greatly increased in its demands as an optical detecting device of high speed communication network because it is used for signal detecting of optical communication, and signal detecting for communication between the Earth and satellite, and between satellites, and also, as communication detecting device in the atmosphere of the Earth and cosmic space with the advent of the aerospace time.
  • an optical amplifier or a silicon optical diode is being used for an ultraviolet rays detecting device.
  • the optical amplifier has disadvantages in that it requires a high voltage and its efficiency is low.
  • the silicon optical diode also has disadvantages in that it is sensitive to visible rays and infrared rays and a band control filtering device should be added, so that the bulk of the detecting device becomes big, and its structure is very complex.
  • silicon since silicon has a narrow band gap, it has a problem of thermal stability, and further in a bad environmental condition, it shows a disadvantage of chemical unstableness .
  • it should be necessary to use a semiconductor which is stable thermally and chemically, and has low sensitivity to the ranges of visible rays and infrared rays.
  • a zinc oxide compound becomes an object for many experimental researches as a material effectively to replace the material of a conventional ultraviolet detecting device since it has many advantages of chemical and thermal stability, high mobility, high quantum effect, and selectivity of specific wave length according to the molar fraction control of added Mg, etc. as a maximum band gap semiconductor of direct transition type.
  • the zinc oxide has many advantages as above, it is difficult to form a zinc oxide thin film having a hole concentration higher than 10 19 /cm 3 effectively by the conventional technology.
  • a zinc oxide thin film used as an optical material is required to have a high quality of crystallinity and uniformity.
  • MOCVD metal organic CVD
  • molecular beam epitaxy and pulse laser deposition method, etc. have been used, but all of them have a disadvantage of being very costly.
  • the present invention is directed to a p-type zinc oxide thin film having a hole concentration higher than 10 x /cm 3 that substantially obviates one or more problems due to limitations and disadvantages of the related art.
  • An object of the present invention is to provide a method of manufacturing an optical power compound semiconductor device formed by dual-doping a material of a substrate into a zinc oxide thin film which is deposited on the substrate, and is made of different dopant materials from the material of the substrate.
  • Another object of the present invention is to provide a p-type zinc oxide thin film manufactured by using a sputtering method to decrease production cost, and a manufacturing method thereof.
  • an optoelectronic oxide semiconductor device includes a substrate, and a film of
  • the film of ZnO ⁇ .. (O ⁇ X ⁇ l) of the present invention contains a p-type dopant and an n-type dopant, and has a hole concentration higher than at least 10 19 /cm 3 .
  • the film has a mobility higher than 12 cm 2 /V-sec, and a resistivity lower than 0.012 ⁇ -cm.
  • the p-type dopant is selected from the group N elements, and preferably contains As.
  • the n- type dopant is selected from the group IE elements, and preferably includes Ga .
  • the substrate may be made of GaAs.
  • the thickness of the film of ZnO ⁇ (0 ⁇ X ⁇ 1) is greater than 0.3 ⁇ , and the molar ratio of the Ga and the As contained in the film is controlled to be in a range of 0.0001 - 0.1.
  • the p-type zinc oxide thin film of the present invention may be used in a p-n junction, an electric field transistor, a light-emitting diode, a laser diode or a light-detecting diode.
  • a manufacturing method of a p-type zinc oxide thin film may be performed by loading a GaAs substrate into a reaction chamber under a vacuum condition, depositing a zinc oxide thin film on the GaAs substrate to a predetermined thickness, thermally annealing the substrate on which the zinc oxide thin film is deposited so that the Ga atom and the As atom of the GaAs substrate are dual-doped into the zinc oxide thin film to control a concentration of the thin film.
  • the deposition and the thermal-annealing of the zinc oxide thin film can be performed by one selected from the group consisting of MBE, MOCVD, PLD and a sputtering apparatus.
  • the deposition of the zinc oxide thin film can be performed by a magnetron sputtering by using a ZnO target, or by a reactive ion sputtering using a Zn target, and Ar gas and 0 2 gas are fed into the reaction chamber for a sputtering in each case.
  • the deposition and the thermal-annealing of the zinc oxide thin film can be performed at a room temperature or higher than that, and the thermal annealing of the zinc oxide thin film can be performed by sealing the reaction chamber at a high vacuum pressure higher than about 10 ⁇ 3 Torr and thermally annealing the zinc oxide thin film in the atmospheric condition, or can be performed under an environment of a high vacuum pressure higher than about 10 " 2 Torr without sealing or under an environment in which an atmosphere can be controllable.
  • the zinc oxide thin film may have a hole concentration higher than at least 10 19 /cm 3 , a mobility higher than 12 cnr/V-sec, and a resistivity not greater than 0.012 ⁇ -cm.
  • the thermal-annealing is performed at a temperature of about 300 - 750 °C for several minutes to several hours.
  • FIG. 1 is a schematic diagram of a magnetron sputtering apparatus which is applied on a manufacturing method of a zinc oxide thin film in accordance with the present invention
  • FIG. 2 is a schematic diagram of a quartz furnace for annealing a zinc oxide thin film formed by using the apparatus of FIG. 1;
  • FIGs. 3a and 3b are SEM photographs of zinc oxide thin films manufactured by the method of the present invention.
  • FIG. 4 is a graphical representation of the analysis results by an X-ray diffraction in cases of depositing a zinc oxide thin film, and annealing after the deposition of the zinc oxide thin film formed by the manufacturing method of the present invention
  • FIG. 5 is a view of the photoluminescence characteristic spectrums of zinc oxide thin films in cases of depositing a zinc oxide thin film, and annealing after the deposition of the zinc oxide thin film respectively formed by the manufacturing method of the present invention
  • FIG. 6 is a view of a secondary ion mass spectrometry (SIMS) characteristic spectrum of a zinc oxide thin film formed by the manufacturing method of the present invention.
  • SIMS secondary ion mass spectrometry
  • FIG. 7 is a table showing hole concentration, mobility, and resistivity measured after forming a zinc oxide semiconductor device formed by the manufacturing method of the present invention.
  • FIG. 1 is a schematic diagram of a magnetron sputtering apparatus which is applied on a manufacturing method of a zinc oxide thin film in accordance with the present invention.
  • a magnetron sputtering apparatus 100 includes a reaction chamber 110. Inside the reaction chamber 110, a substrate holder 120, on which a substrate 200 is placed, is located inside the reaction chamber 110 with adjacent to the upper surface of the reaction chamber 110, and a zinc oxide thin film is deposited on the substrate 200.
  • a sputter gun 130 is placed on the lower side of the reaction chamber 110, and a ZnO target 210 of a high degree of purity is placed on the sputter gun 130.
  • a pumping part 140 is connected on a predetermined portion of the reaction chamber 110 (the right side in FIG. 1) for purging the reaction chamber 110 and controlling the pressure inside the reaction chamber 110.
  • the pumping part 140 includes a rotary pump and a diffusion pump.
  • a gas supplying part 150 is placed on a predetermined portion of the reaction chamber 110 (the left side in FIG. 1) for supplying reaction gases to generate plasma, and a MFC (mass flow controller) 152 is placed on a gas supplying pipe of the gas supplying part 150, for controlling the flow of supplied gas.
  • the sputter gun 130 is connected to an RF (radio frequency) matching box 160, and the RF matching box 160 is connected to a RF power source 170.
  • a plasma shield 180 is placed on the edge portion of the sputter gun 130, for preventing the plasma generated from the sputter gun 130 from proceeding toward the edge portion of the reaction chamber 110.
  • the GaAs substrate 200 is placed on the substrate holder 120 inside the reaction chamber 110 to form a zinc oxide thin film, and the ZnO target 210 is placed on the sputter gun 130. That is, the target 210 and the substrate 200 are placed to face each other.
  • the pumping part 140 extracts the air inside the reaction chamber 110 to maintain the pressure inside the reaction chamber 110 at 10 "3 Torr and over that.
  • Ga and As are used as a dual- doped material into the zinc oxide thin film and thus, the GaAs substrate is used, but to dope other kinds of materials, a substrate of InP, GaN, or A1N, etc. can be used.
  • Ar gas and 0 2 gas are fed into the reaction chamber 110 by the gas supplying part 150 through separate supplying pipes.
  • the MFC 152 functions to control the amount of the supplied Ar gas and 0 2 gas.
  • RF energy is supplied to the sputter gun 130 to ionize the mixture of the Ar gas and 0 2 gas to generate plasma.
  • Ionized Ar and 0 2 ions inside the generated plasma strike the target and sputter the target material so that a zinc oxide thin film is deposited on the substrate 200.
  • a substrate 202 which is produced with the zinc oxide thin film formed thereon as a result of the sputtering, is introduced into a quartz tube or a container which is separated from the outer atmosphere, or possibly controls its inner atmosphere for thermal- annealing.
  • the substrate 202 is annealed at a temperature of, for example, about 300 °C or higher than that, preferably a temperature range of 300 - 750 °C with varying time intervals in accordance with an appropriate doping concentration .
  • the reason that 0 2 gas and Ar gas are supplied together is to control a stoichiometric ratio of the zinc oxide thin film which is formed on the substrate by the sputtering method from the ZnO target .
  • a Zn target is used instead of the ZnO target to separate Zn ions from the Zn target, to react the separated Zn ions with supplied 0 2 ions, and to form a zinc oxide thin film on a substrate.
  • the above embodiment introduces about the sputtering of the zinc oxide thin film which is performed at a room temperature as an example, but a preheating of the substrate up to a predetermined temperature can be additionally performed before the deposition of the thin film to increase the dual doping effect of Ga and As.
  • FIGs . 3a and 3b are SEM photographs of the zinc oxide thin films formed by the manufacturing method of the present invention wherein the photographs show the cases of supplying Ar gas only, and supplying Ar gas and 0 2 gas together respectively when using the ZnO target.
  • grain size is much more precisely shown in FIG. 3b where 0 2 gas is supplied with Ar gas, than the case in FIG. 3a where Ar gas only is supplied.
  • FIG. 4 is a graphical representation of the analysis results by an X-ray diffraction in cases of depositing a zinc oxide thin film, and annealing after the deposition of the zinc oxide thin film respectively formed by the manufacturing method of the present invention. In two cases, a peak is shown when 2 ⁇ is about 35°by which it is confirmed that a formed film is a zinc oxide thin film preferentially grown in the direction of c axis.
  • FIG. 5 is a view of the photoluminescence characteristic spectrums of zinc oxide thin films in cases of depositing a zinc oxide thin film, and annealing after the deposition of the zinc oxide thin film respectively formed by the manufacturing method of the present invention.
  • a peak is generated at about 430 nm of wavelength in both cases by which it is confirmed that a formed film is a zinc oxide thin film.
  • FIG. 6 is a view of a characteristic spectrum by secondary ion mass spectrometry (SIMS) using Cs + as primary ion for a zinc oxide thin film deposited by the above manufacturing method and annealed.
  • SIMS secondary ion mass spectrometry
  • the amount of secondary ions, Ga and As is constant up to about 0.8 ⁇ m in thickness, but is rapidly increased at the thickness higher than 0.8 ⁇ .
  • the portion above 0.8 ⁇ m is found to be a GaAs substrate, and therefore, it is presumed that the thickness of the zinc oxide thin film formed on the GaAs substrate is about 0.8 ⁇ m.
  • the above result apparently shows that Ga atom and As atom are diffused into the zinc oxide thin film and dual- doped during a thermal-annealing.
  • FIG. 7 is a table showing hole concentration, mobility, and resistivity measured on the zinc oxide thin film deposited and then, annealed by the manufacturing method of the present invention.
  • the zinc oxide thin film (sample A ⁇ D) manufactured by the dual-doping of As and Ga ions during a thermal-annealing has a hole concentration of 1.2
  • a p-type zinc oxide thin film having a hole concentration above 10 19 /cm 3 can be achieved by dual-doping a group IE element and a group N element, Ga and As, into a zinc oxide thin film because the introduction of an n-type dopant, a group III element reduces Madelung energy, and the incorporation with a p- type dopant, a group N element is made easy to enhance the local energy level of As inside a band gap.
  • the p-type zinc oxide manufactured by the embodiment of the present invention is different from a p-type zinc oxide which is conventionally produced by doping As only, wherein an As doping concentration does not explain a hole concentration higher than 10 18 /cm 3 and 10 20 /cm 3 .
  • an As doping concentration does not explain a hole concentration higher than 10 18 /cm 3 and 10 20 /cm 3 .
  • the mechanism of dual doping of Ga and As according to the present invention can fully explain the above result.
  • a zinc oxide thin film of the present invention Ga and As atoms, components of a GaAs substrate are diffused and dual-doped into a zinc oxide thin film formed on the substrate during a thermal-annealing.
  • a p-type zinc oxide thin film is achieved with a hole concentration higher than 10 19 /cm 3 and characteristics of the p-type zinc oxide thin film.

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  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Optics & Photonics (AREA)
  • Physical Deposition Of Substances That Are Components Of Semiconductor Devices (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

L'invention concerne un dispositif à semiconducteur doté d'un film mince en oxyde zinc, qui présente une concentration en trous supérieure à 1019/cm3. L'élaboration de ce film résulte d'un dopage à double dopant (élément du groupe III, Ga, et élément du groupe V, As). L'objectif est de réduire l'énergie de Madelung en faisant intervenir un élément du groupe III, dopant de type n, et un élément du groupe V, dopant de type p, dont l'incorporation est facilitée de manière à augmenter le niveau d'énergie locale de l'élément As à l'intérieur d'une largeur de bande interdite.
PCT/KR2002/001952 2001-10-19 2002-10-18 Film mince en oxyde de zinc de type p, compose semiconducteur dote de ce film, et procede de fabrication correspondant WO2003034510A1 (fr)

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KR1020010064670A KR20030033228A (ko) 2001-10-19 2001-10-19 p형 아연산화물 박막과 이를 적용한 화합물 반도체 및 그 제조방법
KR2001/64670 2001-10-19

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Cited By (2)

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CN100355657C (zh) * 2005-09-29 2007-12-19 江苏大学 同轴送氧激光原位制备氧化锌纳米晶体的方法和装置
CN100448778C (zh) * 2005-10-27 2009-01-07 江苏大学 基于连续激光或红外线制备氧化锌纳米晶体的方法和装置

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KR100698588B1 (ko) * 2005-05-30 2007-03-22 원광대학교산학협력단 앰플-튜브 법을 이용한 인과 비소 도핑 피형 산화아연 박막제조방법
KR100909564B1 (ko) * 2005-12-23 2009-07-27 주식회사 삼양사 스퍼터링 증착 장치

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WO2001043165A2 (fr) * 1999-11-12 2001-06-14 The Curators Of The University Of Missouri Pellicules d'oxyde de zinc contenant un dopant de type p et procede de fabrication de ces pellicules
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JP4126332B2 (ja) * 1999-08-13 2008-07-30 学校法人高知工科大学 低抵抗ｐ型単結晶酸化亜鉛およびその製造方法
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EP1030378A2 (fr) * 1999-02-19 2000-08-23 Murata Manufacturing Co., Ltd. Element semi-conducteur luminescent et méthode de fabrication
WO2001043165A2 (fr) * 1999-11-12 2001-06-14 The Curators Of The University Of Missouri Pellicules d'oxyde de zinc contenant un dopant de type p et procede de fabrication de ces pellicules
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Cited By (2)

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CN100355657C (zh) * 2005-09-29 2007-12-19 江苏大学 同轴送氧激光原位制备氧化锌纳米晶体的方法和装置
CN100448778C (zh) * 2005-10-27 2009-01-07 江苏大学 基于连续激光或红外线制备氧化锌纳米晶体的方法和装置

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