CN101538734A - Method for growing Zn(1-x)MgxO crystal thin film on Si substrate - Google Patents

Method for growing Zn(1-x)MgxO crystal thin film on Si substrate Download PDF

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CN101538734A
CN101538734A CN200910096793A CN200910096793A CN101538734A CN 101538734 A CN101538734 A CN 101538734A CN 200910096793 A CN200910096793 A CN 200910096793A CN 200910096793 A CN200910096793 A CN 200910096793A CN 101538734 A CN101538734 A CN 101538734A
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CN101538734B (en
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潘新花
叶志镇
潘晓晴
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Zhejiang University ZJU
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Abstract

The invention discloses a method for growing a Zn(1-x)MgxO crystal thin film on a Si substrate, a Lu2O3, Sc2O3 or Gd2O3 single crystal thin film buffer layer is firstly epitaxially grown on the Si substrate, then the pulsed laser deposition method is adopted, a Zn(1-x)MgxO ceramic target is taken as a target material, x is more than 0 and not more than 30 percent, a Zn(1-x)MgxO thin film is deposited on the Si substrate with the buffer layer, and the deposition of the Zn(1-x)MgxO thin film is divided into two steps: a Zn(1-x)MgxO nuclear layer with the thickness of 5-15mm is firstly deposited at 200-280 DEG C, then the temperature is increased to 500-700 DEG C, and the Zn(1-x)MgxO thin film is deposited. The method realizes the epitaxial growth of the Zn(1-x)MgxO crystal thin film on the Si substrate by firstly epitaxially growing the single crystal thin film buffer layer on the Si substrate, the method is simple, and the prepared Zn(1-x)MgxO crystal thin film has excellent structural performance, optical performance and electrical performance.

Description

Zn grows on the Si substrate 1-xMg xThe method of O crystal film
Technical field
The present invention relates to Zn 1-xMg xZn grows on the growth method of O crystal film, especially the Si substrate 1-xMg xThe method of O crystal film.
Background technology
ZnO is the direct band-gap semicondictor material, and its room temperature energy gap is 3.37eV, and the room-temperature exciton bound energy is 60meV, is the ideal material of photoelectric devices such as preparation blue light-ultraviolet light-emitting diodes and laser apparatus.In order to research and develop the zno-based photoelectric device, an important step realizes the ZnO energy band engineering exactly, thereby realizes in the photoelectric device the dual constraint effect to electronics and photon.The application of ZnO in uv electron optics, key is the growth of heterojunction structure and quantum well, reach this purpose, the band gap of material is regulated just to seem very important when keeping lattice parameter close.Mg 2+Ionic radius
Figure A20091009679300031
With Zn 2+Ionic radius
Figure A20091009679300032
Very approaching, in the ZnO film process of growth, add a certain amount of Mg, the Zn of acquisition 1-xMg xThe O alloy has the crystalline structure identical with ZnO, the relative ZnO broadening of energy gap, and lattice parameter changes not quite.Therefore, Zn 1-xMg xThe O alloy is the preferred material of carrying out the ZnO energy band engineering.
Zn grows on the Si single crystalline substrate 1-xMg xThe O crystal film more helps making electric injection device, because Si has good electroconductibility.Can make full use of sophisticated Si planar technology of semi-conductor industry and photoetching technique like this, the photoelectricity that helps the ZnO device is integrated, and Zn therefore grows on the Si substrate 1-xMg xThe O crystal film has broad application prospects.
Yet, because Si and Zn 1-xMg xHave bigger lattice mismatch and thermal mismatching between the O, the Si surface is easy to oxidation simultaneously, therefore is difficult to realize directly epitaxy Zn on the Si substrate 1-xMg xThe O alloy firm.
Summary of the invention
The purpose of this invention is to provide a kind of Zn that on the Si substrate, grows 1-xMg xThe method of O crystal film.
Zn grows on the Si substrate of the present invention 1-xMg xThe method of O crystal film may further comprise the steps:
The ZnO of 1) weighing purity 〉=99.99% and MgO powder, wherein the molar content x of Mg is 0＜x≤30%, with above-mentioned powder ball milling mix, compression moulding, at 1000～1300 ℃ of sintering temperatures, make Zn then 1-xMg xThe O ceramic target;
2) adopt the reaction molecular beam epitaxy method Y that on the Si substrate, grows 2O 3The monocrystal thin films buffer layer, Y 2O 3Be Lu 2O 3Or Sc 2O 3Or Gd 2O 3, buffer layer thickness is 30～100nm, growth conditions: with the Y source is reaction source, 650～750 ℃ of underlayer temperatures, and regulating growth room's oxygen pressure is 1 * 10 -6Torr～3 * 10 -6Torr;
3) ceramic target that step 1) is made and the Y that has through cleaning 2O 3The Si substrate of buffer layer is put into pulsed laser deposition device growth room, and the distance between target and the substrate remains 4～6cm, and growth room's vacuum tightness is evacuated to 3.75 * 10 at least -9Torr, at first substrate is heated to 200～280 ℃, and the growth room feeds purity oxygen, and regulating the oxygen pressure is 5 * 10 -3Torr～40 * 10 -3Torr opens laser apparatus, allows laser beam focus on target surface ablation target, forms twilight sunset, the thick Zn of deposition one deck 5～15nm on substrate 1-xMg xO forming core layer is warming up to 500～700 ℃ then, keeps oxygen to press, and opens laser apparatus once more, allows laser beam focus on target surface ablation target, forms twilight sunset, at Zn 1-xMg xDeposit on the O forming core layer, make Zn 1-xMg xThe O crystal film is cooled to room temperature with film under oxygen atmosphere.
The purity of above-mentioned pure oxygen is more than 99.99%.Said Si substrate is (111) Si single crystalline substrate.Zn 1-xMg xMg content can be controlled by the molar content of regulating Mg in the target in the O film.Growth time is by the thickness decision of required crystal film.
Beneficial effect of the present invention is:
1) method is simple, controls Zn by the molar content of regulating Mg in the target 1-xMg xMg content in the O film, thus realize the adjusting of ZnO band gap in 3.3～4.0eV scope;
2) by first epitaxy one deck Y on the Si substrate 2O 3The monocrystal thin films buffer layer has been realized epitaxy Zn on the Si substrate 1-xMg xThe O crystal film;
3) Zn that makes of the present invention 1-xMg xThe O crystal film has good structure properties, optical property and electric property.
Description of drawings
Fig. 1 is Zn 0.9Mg 0.1X ray diffraction (XRD) collection of illustrative plates of O crystal film;
Fig. 2 is Zn 0.9Mg 0.1The photoluminescence of O crystal film (PL) collection of illustrative plates.
Embodiment
The present invention is further illustrated by example below in conjunction with accompanying drawing.Concrete steps are as follows:
Embodiment 1
1) the preparation weighing purity in proportion of ceramic target is 99.999% ZnO and MgO powder, and wherein the molar content of Mg is 10%.Load weighted ZnO and MgO powder are poured in the ball grinder that agate ball is housed, and ball milling is 18 hours on ball mill, and purpose is with ZnO and the evenly also refinement to a certain extent of MgO powder mixes.Then raw material is separated and dried, grind compression moulding.The idiosome of moulding is put into sintering oven, be warming up to 1300 ℃ of sintering 8 hours, obtain Zn 0.9Mg 0.1The O ceramic target.
2) reaction molecular beam epitaxy method is adopted in the growth of buffer layer, and substrate is heated to 700 ℃, and regulating growth room's oxygen pressure is 2 * 10 -6Torr, the reaction source of employing are the Lu source, and Lu grows on (111) Si single crystalline substrate 2O 3Monocrystal thin films, the control film thickness is about 30nm;
3) Zn 0.9Mg 0.1The preparation of O film is with Zn 0.9Mg 0.1The O ceramic target is contained on the target frame, embeds then in the target holder of pulsed laser deposition device.With step 2) growth have thick (111) Lu of 30nm 2O 3(111) Si single crystalline substrate of buffer layer is fixed on the sample table after cleaning, and puts into the growth room.The distance of regulating substrate and target is 4.5cm, and with baffle plate substrate and target is separated.Growth room's vacuum tightness is evacuated to 3 * 10 -9Torr, heated substrate in heat-processed, is opened laser apparatus (pulsed laser energy is 100mJ, frequency 5Hz), and pre-sputter 10min removes staining of target material surface.Zn 0.9Mg 0.1The O film growth is in two steps: at first substrate is heated to 240 ℃, and the growth room feeds pure O 2, regulating the oxygen pressure is 5 * 10 -3Torr, the baffle plate of outwarding winding, the thick Zn of deposition one deck 10nm 0.9Mg 0.1O forming core layer is warming up to 600 ℃ then, keeps oxygen to press, deposition Zn 0.9Mg 0.1The O film.Substrate and target low speed rotation in the deposition process are to improve the homogeneity of film.Depositing time is 60min, the thick 500nm that is about of film.The growth ending rear film slowly cools to room temperature under former growth atmosphere.
Above-mentioned Zn 0.9Mg 0.1The room temperature electric property of O crystal film is good: resistivity is that 4 sub-concentration are 8.8 * 10 16Cm -3, hall mobility is 17cm 2/ V.s.And considerable change does not take place in the electric property of placing several months rear film.
X ray diffraction (XRD) collection of illustrative plates of above-mentioned film as shown in Figure 1, removes from substrate (111) Si and buffer layer (111) Lu 2O 3Strong diffraction peak outer (* represents the diffraction peak of substrate), have three peaks, correspond respectively to Zn 0.9Mg 0.1(0002) of O, (0004) and (0006) diffraction surfaces shows the Zn that the inventive method makes 0.9Mg 0.1The O crystal film has good crystal property; XRD does not detect second mutually as relevant diffraction peaks such as MgO simultaneously, shows Zn 0.9Mg 0.1The O film is single hexagonal wurtzite structure.
Fig. 2 is 10K photoluminescence (PL) collection of illustrative plates of above-mentioned film.As seen from the figure, film has very strong ultraviolet band-edge luminescence peaks (NBE), shows the Zn that the inventive method makes 0.9Mg 0.1The O crystal film has the good optical performance.In addition, tangible blue shift has taken place with respect to the peak position of pure ZnO in the peak position 3.558eV of its ultraviolet band-edge luminescence peaks, illustrates that Mg has entered into the ZnO lattice really and formed Zn 0.9Mg 0.1The O alloy crystal, thus make being with of ZnO that broadening take place, play the effect that adjusting can be with.
Embodiment 2
1) the preparation weighing purity in proportion of ceramic target is 99.999% ZnO and MgO powder, and wherein the molar content of Mg is 30%.Load weighted ZnO and MgO powder are poured in the ball grinder that agate ball is housed, and ball milling is 20 hours on ball mill, and purpose is with ZnO and the evenly also refinement to a certain extent of MgO powder mixes.Then raw material is separated and dried, grind compression moulding.The idiosome of moulding is put into sintering oven, be warming up to 1200 ℃ of sintering 8 hours, obtain Zn 0.7Mg 0.3The O ceramic target.
2) reaction molecular beam epitaxy method is adopted in the growth of buffer layer, and substrate is heated to 750 ℃, and regulating growth room's oxygen pressure is 3 * 10 -6Torr, the reaction source of employing are the Sc source, and Sc grows on (111) Si single crystalline substrate 2O 3Monocrystal thin films, the control film thickness is about 60nm;
3) Zn 0.7Mg 0.3The preparation of O film is with Zn 0.7Mg 0.3The O ceramic target is contained on the target frame, embeds then in the target holder of pulsed laser deposition device.With step 2) growth have thick (111) Sc of 60nm 2O 3(111) Si single crystalline substrate of buffer layer is fixed on the sample table after cleaning, and puts into the growth room.The distance of regulating substrate and target is 5cm, and with baffle plate substrate and target is separated.Growth room's vacuum tightness is evacuated to 3 * 10 -9Torr, heated substrate in heat-processed, is opened laser apparatus (pulsed laser energy is 100mJ, frequency 5Hz), and pre-sputter 10min removes staining of target material surface.Zn 0.7Mg 0.3The O film growth is in two steps: at first substrate is heated to 200 ℃, and the growth room feeds pure O 2, regulating the oxygen pressure is 40 * 10 -3Torr, the baffle plate of outwarding winding, the thick Zn of deposition one deck 10nm 0.7Mg 0.3O forming core layer is warming up to 680 ℃ then, keeps oxygen to press, deposition Zn 0.7Mg 0.3The O film.Substrate and target low speed rotation in the deposition process are to improve the homogeneity of film.Depositing time is 60min, the thick 500nm that is about of film.The growth ending rear film slowly cools to room temperature under former growth atmosphere.
Above-mentioned Zn 0.7Mg 0.3The room temperature electric property of O crystal film is good: resistivity is 20.95 Ω cm, and carrier concentration is 1.5 * 10 16Cm -3, hall mobility is 19.8cm 2/ V.s.And considerable change does not take place in the electric property of placing several months rear film.
Embodiment 3
1) the preparation weighing purity in proportion of ceramic target is 99.999% ZnO and MgO powder, and wherein the molar content of Mg is 20%.Load weighted ZnO and MgO powder are poured in the ball grinder that agate ball is housed, and ball milling is 20 hours on ball mill, and purpose is with ZnO and the evenly also refinement to a certain extent of MgO powder mixes.Then raw material is separated and dried, grind compression moulding.The idiosome of moulding is put into sintering oven, be warming up to 1250 ℃ of sintering 8 hours, obtain Zn 0.8Mg 0.2The O ceramic target.
2) reaction molecular beam epitaxy method is adopted in the growth of buffer layer, and substrate is heated to 700 ℃, and regulating growth room's oxygen pressure is 1 * 10 -6Torr, the reaction source of employing are the Gd source, and Gd grows on (111) Si single crystalline substrate 2O 3Monocrystal thin films, the control film thickness is about 100nm;
3) Zn 0.8Mg 0.2The preparation of O film is with Zn 0.8Mg 0.2The O ceramic target is contained on the target frame, embeds then in the target holder of pulsed laser deposition device.With step 2) growth have thick (111) Gd of 100nm 2O 3(111) Si single crystalline substrate of buffer layer is fixed on the sample table after cleaning, and puts into the growth room.The distance of regulating substrate and target is 5cm, and with baffle plate substrate and target is separated.Growth room's vacuum tightness is evacuated to 3 * 10 -9Torr, heated substrate in heat-processed, is opened laser apparatus (pulsed laser energy is 100mJ, frequency 5Hz), and pre-sputter 10min removes staining of target material surface.Zn 0.8Mg 0.2The O film growth is in two steps: at first substrate is heated to 280 ℃, and the growth room feeds pure O 2, regulating the oxygen pressure is 20 * 10 -3Torr, the baffle plate of outwarding winding, the thick Zn of deposition one deck 10nm 0.8Mg 0.2O forming core layer is warming up to 550 ℃ then, keeps oxygen to press, deposition Zn 0.8Mg 0.2The O film.Substrate and target low speed rotation in the deposition process are to improve the homogeneity of film.Depositing time is 60min, the thick 500nm that is about of film.The growth ending rear film slowly cools to room temperature under former growth atmosphere.
Above-mentioned Zn 0.8Mg 0.2The room temperature electric property of O crystal film is good: resistivity is 28.82 Ω cm, and carrier concentration is 1.68 * 10 16Cm -3, hall mobility is 12.9cm 2/ V.s.And considerable change does not take place in the electric property of placing several months rear film.

Claims (2)

  1. The Zn 1.Si grow on the substrate 1-xMg xThe method of O crystal film is characterized in that may further comprise the steps:
    The ZnO of 1) weighing purity 〉=99.99% and MgO powder, wherein the molar content x of Mg is 0＜x≤30%, with above-mentioned powder ball milling mix, compression moulding, at 1000～1300 ℃ of sintering temperatures, make Zn then 1-xMg xThe O ceramic target;
    2) adopt the reaction molecular beam epitaxy method Y that on the Si substrate, grows 2O 3The monocrystal thin films buffer layer, Y 2O 3Be Lu 2O 3Or Sc 2O 3Or Gd 2O 3, buffer layer thickness is 30～100nm, growth conditions: with the Y source is reaction source, 650～750 ℃ of underlayer temperatures, and regulating growth room's oxygen pressure is 1 * 10 -6Torr～3 * 10 -6Torr;
    3) ceramic target that step 1) is made and the Y that has through cleaning 2O 3The Si substrate of buffer layer is put into pulsed laser deposition device growth room, and the distance between target and the substrate remains 4～6cm, and growth room's vacuum tightness is evacuated to 3.75 * 10 at least -9Torr, at first substrate is heated to 200～280 ℃, and the growth room feeds purity oxygen, and regulating the oxygen pressure is 5 * 10 -3Torr～40 * 10 -3Torr opens laser apparatus, allows laser beam focus on target surface ablation target, forms twilight sunset, the thick Zn of deposition one deck 5～15nm on substrate 1-xMg xO forming core layer is warming up to 500～700 ℃ then, keeps oxygen to press, and opens laser apparatus once more, allows laser beam focus on target surface ablation target, forms twilight sunset, at Zn 1-xMg xDeposit on the O forming core layer, make Zn 1-xMg xThe O crystal film is cooled to room temperature with film under oxygen atmosphere.
  2. 2. Zn grows on the Si substrate according to claim 1 1-xMg xThe method of O crystal film is characterized in that said Si substrate is (111) Si single crystalline substrate.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102031487A (en) * 2010-10-11 2011-04-27 深圳大学 Hexagonal MgZnO film with high magnesium content and preparation method thereof
CN103922387A (en) * 2014-03-28 2014-07-16 苏州科技学院 Magnetic zinc oxide nano wire and preparation method thereof
CN111822886A (en) * 2020-06-11 2020-10-27 华东师范大学重庆研究院 Multi-focus ultrafast laser preparation device and method for micro-fluidic chip micro-channel

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100406620C (en) * 2006-05-11 2008-07-30 浙江大学 Li-doped p-Zn1-xMgxO crystal film and method for preparing same
CN100537855C (en) * 2007-08-21 2009-09-09 浙江大学 Sb doped growing p type Zn 1-xMg xThe method of O crystal film

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102031487A (en) * 2010-10-11 2011-04-27 深圳大学 Hexagonal MgZnO film with high magnesium content and preparation method thereof
CN103922387A (en) * 2014-03-28 2014-07-16 苏州科技学院 Magnetic zinc oxide nano wire and preparation method thereof
CN103922387B (en) * 2014-03-28 2016-01-20 苏州科技学院 A kind of magnetic nanometic zinc oxide line and preparation method thereof
CN111822886A (en) * 2020-06-11 2020-10-27 华东师范大学重庆研究院 Multi-focus ultrafast laser preparation device and method for micro-fluidic chip micro-channel

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