CN100424825C - Method for making the growth ZnO thin film material with the covariant underlay - Google Patents
Method for making the growth ZnO thin film material with the covariant underlay Download PDFInfo
- Publication number
- CN100424825C CN100424825C CNB2006100030727A CN200610003072A CN100424825C CN 100424825 C CN100424825 C CN 100424825C CN B2006100030727 A CNB2006100030727 A CN B2006100030727A CN 200610003072 A CN200610003072 A CN 200610003072A CN 100424825 C CN100424825 C CN 100424825C
- Authority
- CN
- China
- Prior art keywords
- zinc oxide
- substrate
- film material
- oxide film
- preparation
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired - Fee Related
Links
Images
Abstract
The preparation method for ZnO thin film comprises: 1. selecting SOI material with ultrathin silicon monocrystal layer as the silicon-base covariant substrate; 2. putting the sputtering target material into the primary growing room of magnetron sputtering device; 3. pre-sputtering the target surface; 4. putting the cleaned SOI substrate into the primary growing room; 5. heating to roast and remove gas; 6. preparing the ZnO thin film; 7. original annealing; and 8. cooling the sample to room temperature.
Description
Technical field
The present invention relates to technical field of semiconductors, but refer in particular to the method that a kind of utilization has the large scale SOI covariant substrate preparation growing zinc oxide film material of ultra-thin top silicon single crystal layer.
Background technology
Zinc oxide (ZnO) is the short-wavelength light electric device of preparation working and room temperature and the preferred material of spin electric device, and in addition, the ZnO source is abundant, and the prices of raw and semifnished materials are cheap, and the preparation method is relatively simple again, has very good commercial value.Although ZnO is subjected to unprecedented attention both domestic and external in recent years in the research and the application and development of semiconductor applications, but some crucial underlying issues still do not solved at all, such as the single crystal epitaxial growth question and the P type doping problem of high quality ZnO film.And with regard to the single crystal epitaxial problem of ZnO film, except being subjected to the functional limitation of material preparation means, no suitable substrate also is a main obstacles.
Adopting homoepitaxy is the optimal selection that obtains high quality ZnO film, be not difficult to the GaN body monocrystalline obtain though large scale ZnO body monocrystalline does not resemble, but price is very expensive, directly has influence on commercial the application, therefore, still mainly to adopt foreign substrate at present be main to the preparation research of ZnO film.Wherein, silicon (Si) is one of the most frequently used large scale inexpensive substrate of ZnO heteroepitaxial growth.But owing to have big lattice mismatch between Si and ZnO, often gather bigger stress in the preparation-obtained film rete, crystalline quality and surface topography all also are difficult to obtain to improve greatly always, and this greatly limits and influenced the research and the application of Si base ZnO film material.The big mismatch epitaxial problem method relatively more commonly used that solution Si goes up preparation growth ZnO is an employing resilient coating technology, but effect is unsatisfactory.But covariant (flexibility) substrate can be coordinated misfit strain, and reduces and even eliminate the stress of rete inner accumulated, thereby obtains high-quality epitaxial loayer.This class substrate preparation technology plays a significant role in solving some typical big mismatch epitaxial problems.Such as, (Silicon-on-Insulation: growth thin single crystal silicon fiml on insulator) technology prepares and has top ultra-thin Si single crystalline layer/thick middle insulation SiO to utilize the SOI of comparative maturity in the microelectronic component technology
2Layer/bottom Si (100) but the large scale Si base covariant substrate of the three-decker of single crystalline substrate, maximum can reach 12 inches, can coordinate or partly coordinate to prepare on the Si substrate misfit strain of Grown GaN, GaAs, GeSi and SiC homepitaxy layer, both reduce the residual stress of rete inner accumulated, also improved the growth for Thin Film quality.This is because but the top ultra-thin silicon single crystalline layer of SOI material has two essential characteristics of routine covariant (flexibility) layer: (1) top ultra-thin silicon single crystalline layer is by the be altogether unjustifiable crystalline substance or the polycrystalline insulation SiO of centre
2De between buried regions realization and passive Si (100) substrate.Because the SiO of amorphous or polycrystalline under growth or annealing temperature
2The viscosity of middle buried regions is lower, and epitaxial loayer just can pass through Si/SiO
2The plastic deformation at the interface misfit strain that relaxes, thus play the effect of coordinating misfit strain; (2) ultra-thin silicon single crystalline layer in top is thinner, has only tens nanometers, and also smoother is smooth on the surface.
ZnO is the Wideband crack oxide compound semi-conducting material that development in recent years is got up, because of no suitable substrate also is difficult to realize high-quality heteroepitaxial growth so far.But utilize the large scale Si base SOI covariant substrate of development comparative maturity to carry out the ZnO film increment study, can either realize the large area deposition of ZnO material on the Si substrate, also can overcome the oxide contaminant problem that the SOI substrate brings at preparation non-oxidized substance compound semiconductor materials.This respect research work does not at present still also have both at home and abroad, whether can coordinate the misfit strain of the ZnO film material of prepared growth on it for the SOI substrate, and reduce and even eliminate the residual stress in the epitaxial loayer and obtain high-quality epitaxial growth also all not clear.The process means that is used for the ZnO film growth at present is also many, such as molecular beam epitaxy (MBE), metal organic chemical vapor deposition (MOCVD), pulsed laser deposition (PLD) and magnetically controlled sputter method etc., wherein, the magnetically controlled sputter method devices needed and the cost of raw material are cheap, the preparation growth technique is also relatively simple and can realize the large scale growth, has certain application and popularization value.So, if can utilize magnetically controlled sputter method to realize having the ZnO material and ripe silica-based microelectronic component SOI technology perfect adaptation of superior light, electrical property, will lay a good foundation for development New Si base ZnO light, electric device.
Summary of the invention
The invention provides a kind of method for preparing Zinc oxide film material, but be meant that especially a kind of utilization has the large scale SOI covariant substrate of top ultra-thin silicon single crystalline layer, adopt magnetron sputtering apparatus to prepare the method for growing zinc oxide film material.
Purpose is: 1. explore the novel foreign substrate material that is fit to Zinc oxide film material preparation growth, realize its high-quality growth on silicon substrate; 2. the residual stress of the rete inner accumulated of the Zinc oxide film material of development reduction magnetron sputtering apparatus preparation growth has the zinc oxide material of superior photoelectric properties and the ripe basic microelectronic component technology of Si perfect adaptation with new preparation process 3. realizations that improve the film growth quality, lays the foundation for developing novel opto-electronic device.The technical scheme that technical solution problem of the present invention is adopted is:
A kind of method for preparing Zinc oxide film material is provided, but utilizes large scale SOI covariant substrate, adopt magnetron sputtering apparatus to prepare growing zinc oxide film with ultra-thin top silicon single crystal layer.But preliminary treatment by SOI covariant substrate before growing and sputtering target, the regulation and control of sputtering power, working gas and reacting gas proportioning, operating air pressure and growth temperature during growth, and the annealing in process after the growth, realize the height C axle preferrel orientation growth of Zinc oxide film material on silicon substrate, and residual stress reduces in the rete, and crystalline quality and surface topography improve.And then make Zinc oxide film material and ripe silica-based microelectronic component SOI technology perfect adaptation with superior light, electrical property, for develop novel light, electric work can lay the foundation by device.
But the described SOI covariant substrate that utilizes adopts magnetron sputtering apparatus to prepare the method for Zinc oxide film material, wherein, comprises the steps:
Step 1: select for use the top to have the SOI material of ultra-thin silicon single crystalline layer as the silicon based compliant substrate;
Step 2: with the sputtering target material primary growing room of magnetron sputtering device of packing into;
Step 3: the pre-sputter process in surface of carrying out sputtering target material;
Step 4: the main growth room of magnetron sputtering apparatus but the SOI covariant substrate that will clean is packed into;
Step 5: but carry out the heated baking degassing processing of SOI covariant substrate;
Step 6: the magnetically controlled sputter method preparation growth of Zinc oxide film material;
Step 7: the in-situ annealing of Zinc oxide film material is handled;
Step 8: the zinc oxide sample that will drop to room temperature is taken out.
Described preparation Zinc oxide film material method, wherein the SOI material described in the step 1 is that the top of adopting the preparation of energetic oxygen ions method for implanting has the thick ultra-thin Si single crystalline layer of 10 ~ 50nm, the centre has 200 ~ 600nm thick silicon oxide insulating barrier and the bottom has the three-decker large scale SOI material that (100) are orientated silicon monocrystalline substrate.
Described preparation Zinc oxide film material method, wherein the sputtering target material in the step 3 is a purity greater than 99.99% metallic zinc and zinc oxide material.
Described preparation Zinc oxide film material method, metallic zinc target wherein are to adopt the dc reactive sputtering method to carry out the Zinc oxide film material preparation.
Described preparation Zinc oxide film material method, zinc oxide target wherein are to adopt the interchange RF sputtering method to carry out the Zinc oxide film material preparation.
Described preparation Zinc oxide film material method, wherein, distance between metallic zinc target and substrate is 5-7cm, the reactive sputtering power of DC power supply is 40-60W, the flowrate proportioning of working gas argon gas and reacting gas oxygen is 1: 4-1: 3, and the air pressure of always working is 0.5-1.0Pa, underlayer temperature is 350-550 ℃, pre-growth and growth time are respectively 1-3 and 180-210 minute, and at 700-750 ℃ of following in-situ annealing 20-30 minute.
Described preparation Zinc oxide film material method, wherein, the distance of zinc oxide target and substrate is 6-8cm, the sputtering power that exchanges radio-frequency power supply is 80-100W, the flowrate proportioning of working gas argon gas and assisted reaction gas oxygen is 4: 1-9: 1, and the air pressure of always working is 0.5-1.0Pa, underlayer temperature is 450-650 ℃, pre-growth and growth time are respectively 1-3 and 180-210 minute, and at 700-750 ℃ of following in-situ annealing 20-30 minute.The present invention compared with prior art has following beneficial effect:
Compare ordinary silicon (Si) substrate, SOI (Si/SiO
2/ Si) but the covariant substrate can be coordinated the misfit strain of zinc oxide (ZnO) thin-film material, and residual stress reduces in the rete, and the crystalline quality of epitaxial loayer and surface topography improvement;
Compare no support substrates, directly or distortion bonded substrate, Pyrex or oxide bonded substrate and Hydrogen induced uncoupled coupling substrate etc. inject by bonding techniques or energetic ion and the thinning technique mode realizes that but but weak bond closes or separate the covariant substrate of coupling between covariant layer and the support substrates, the technology of preparing of SOI substrate is relatively ripe, and can realize the large scale high-quality growth of the ZnO material of big mismatch;
Compare molecular beam epitaxy (MBE), metal organic chemical vapor deposition (MOCVD) and pulsed laser deposition methods such as (PLD), needed raw material of magnetically controlled sputter method and equipment cost are cheap, and preparation technology is also relatively simple, are convenient to realize and promote;
But utilize SOI covariant substrate preparation growing ZnO thin-film, can realize having the broad-band gap zinc oxide semiconductor material of superior photoelectric properties and ripe Si base microelectronic component technology perfect adaptation, lay the foundation for developing novel opto-electronic device.
Description of drawings
For further specifying concrete technology contents of the present invention, below in conjunction with embodiment and accompanying drawing describes in detail as after, wherein:
Rutherford backscattering (RBS) test result of the SOI substrate that Fig. 1, employing energetic oxygen ions injection (SIMOX) method prepare: a empirical curve; The curve that b utilizes Simnra (Version4.0) process simulation to calculate.Curve b that analog computation obtains and empirical curve a coincide very finely, and the top thin Si thickness that analog computation obtains is about 30nm, is sent to a place under guard the silica bed thickness about 5 of coupling
02nm，Si∶O＝1∶2；
Fig. 2, common Si (111) substrate a, Si (100) but on substrate b and the SOI covariant substrate c, adopt atomic force surface topography test analysis (AFM) experimental result of the ZnO film sample that identical dc reactive sputtering prepared obtains;
Fig. 3, common Si (111) substrate a, Si (100) but on substrate b and the SOI covariant substrate c, adopt X-ray diffraction test analysis (XRD) experimental result of the ZnO film sample that identical dc reactive sputtering prepared obtains;
Fig. 4, common Si (111) substrate a, Si (100) but on substrate b and the SOI covariant substrate c, adopt atomic force surface topography test analysis (AFM) experimental result of the ZnO film sample that identical interchange rf magnetron sputtering prepared obtains;
Fig. 5, common Si (111) substrate a, Si (100) but on substrate b and the SOI covariant substrate c, adopt X-ray diffraction test analysis (XRD) experimental result of the ZnO film sample that identical interchange rf magnetron sputtering prepared obtains.
Embodiment
But the important technological parameters of SOI covariant substrate is referring to table 1, adopts experiment parameter that magnetron sputtering apparatus with three sputtering targets prepares growing zinc oxide film material referring to table 2 on it, and it is as follows specifically to prepare growth step:
Step 1: select for use the top to have that the thick ultra-thin silicon single crystalline layer of 10-50nm, centre have 200-600nm thick silicon oxide insulating barrier and the bottom has the three-decker large scale SOI material of silicon monocrystalline substrate of (100) orientation as the silicon based compliant substrate of preparation growing zinc oxide film material.Wherein the SOI material is to adopt energetic oxygen ions to annotate the preparation of (SIMOX) method.
Step 2: select for use purity to be not less than 99.99% metallic zinc or zinc oxide target, take out main growth room vacuum behind the main growth room with its magnetron sputtering apparatus of packing into as the sputtering target target of magnetron sputtering apparatus.
Step 3: primary growing room of magnetron sputtering device vacuum degree is less than 1 * 10
-5Behind the Pa, carry out the pre-sputter process on metallic zinc or zinc oxide target surface.Wherein the pre-sputter in the surface of metallic zinc target is carried out according to the following procedure:
(1) opens the baffle plate of metallic zinc target;
(2) part is closed the slide valve between main growth room and vacuum pump;
(3) logical working gas argon gas in main growth room, the operating air pressure by gas flowmeter elder generation control growing chamber is 1-1.5Pa;
(4) dc supply of opening metal zinc target slowly increases sputtering power to 40-60W, treats in the main growth room behind the metallic zinc target build-up of luminance, reduces the air inflow of working gas argon gas, keeps operating air pressure at 0.5-1.0Pa, pre-sputter 60-90 minute;
(5) close metallic zinc target dc supply, argon gas, block metallic zinc target plate washer, open slide valve between main growth room and vacuum pump fully, take out the vacuum of main growth room.
And the pre-sputter in the surface of zinc oxide target is according to the following procedure:
(1) opens the baffle plate of zinc oxide target;
(2) part is closed the slide valve between main growth room and vacuum pump;
(3) logical working gas argon gas in main growth room, the operating air pressure by gas flowmeter elder generation control growing chamber is 1-1.5Pa;
(4) open the interchange radio frequency operation power supply of zinc oxide target, slowly increase sputtering power, treat that behind the zinc oxide target build-up of luminance, the air inflow of minimizing working gas argon gas is kept operating air pressure at 0.5-1.0Pa, sputter 30-60 minute in advance main the growth room in to 80-120W;
(5) close zinc oxide target and exchange radio frequency operation power supply, argon gas, block the zinc oxide target plate washer, open slide valve between main growth room and vacuum pump fully, take out the vacuum of main growth room.
Step 4: but will clean and with pack into the main growth room of magnetron sputtering apparatus of the SOI covariant substrate that nitrogen dries up.Wherein but the cleaning of SOI covariant substrate is carried out according to the following procedure:
(1) washes repeatedly with deionized water;
(2) with absolute ethyl alcohol ultrasonic cleaning 10-20 minute;
(3) with acetone ultrasonic cleaning 10-20 minute;
(4) with carbon tetrachloride ultrasonic cleaning 10-20 minute;
(5) with acetone ultrasonic cleaning 10-20 minute;
(6) with absolute ethyl alcohol ultrasonic cleaning 10-20 minute;
(7) rinse well repeatedly with deionized water;
(8) pack into before the prechamber of magnetron sputtering apparatus, use the dilute hydrofluoric acid solution rinsing 5-10 second of concentration 1-10% again.
Step 5: the vacuum degree of main growth room reaches 1-5 * 10
-5Behind the Pa, but carry out the heated baking degassing processing of SOI covariant substrate.Wherein, earlier underlayer temperature is raised to 200-300 ℃, toasted 10-20 minute; The vacuum degree of main growth room reaches 1-5 * 10 once more
-5Behind the Pa, underlayer temperature is raised to 650-750 ℃, toasted 20-30 minute; The vacuum degree of main growth room reaches 1-5 * 10 again
-5Behind the Pa, underlayer temperature is dropped to the needed initial temperature of growth, and substrate is sheltered from the substrate baffle plate.
Step 6: the magnetically controlled sputter method preparation growth of Zinc oxide film material.Wherein adopt dc reactive sputtering method preparation growth, carry out according to the following procedure:
(1) distance of adjusting between metallic zinc target and substrate is 5-7cm, opens the baffle plate on this target;
(2) part is closed the slide valve between main growth room and vacuum pump;
(3) first logical working gas argon gas in main growth room, the operating air pressure by gas flowmeter control growing chamber is 1-1.5Pa;
(4) dc supply of opening metal zinc target slowly increases sputtering power to 40-60W, treat the metallic zinc target build-up of luminance in the main growth room after, suitably reduce the air inflow of working gas argon gas, keep operating air pressure at 0.5-1.0Pa;
(5) open the substrate tumbler, set 8-10 rev/min, and open the substrate baffle plate;
(6) but on SOI covariant substrate first sputter one deck zinc of growing in advance, underlayer temperature is 300-400 ℃, grows and shuts the substrate baffle plate after 1-3 minute;
(7) suitably reduce the air inflow of working gas argon gas, and lead to reacting gas oxygen in main growth room, the flow-rate ratio of controlling argon gas and oxygen by gas flowmeter is 1: 4-1: 3, and the air pressure of always working is 0.5-1.0Pa;
(8) open the substrate baffle plate, but adopt the dc reactive sputtering method pre-the growth growing zinc oxide film on the SOI covariant substrate of ultra-thin zinc layer to be arranged, growth temperature is 350-550 ℃, and growth time is determined as required;
(9) close the dc supply of metallic zinc target, stop the preparation growth of Zinc oxide film material, and block the plate washer of metallic zinc target;
(10) stop substrate and rotate, close working gas argon gas and reacting gas oxygen, and open the slide valve between main growth room and vacuum pump fully, take out the vacuum of main growth room.
Adopt to exchange radio frequency magnetron sputtering method preparation growth, carry out according to the following procedure:
(1) distance of adjusting between zinc oxide target and substrate is 6-8cm, opens the baffle plate on this target;
(2) part is closed the slide valve between main growth room and vacuum pump;
(3) first logical working gas argon gas in main growth room, the operating air pressure by gas flowmeter control growing chamber is 1-1.5Pa;
(4) open the interchange radio frequency operation power supply of zinc oxide target, slowly increase sputtering power to 80-100W, treat the zinc oxide target build-up of luminance in the main growth room after, suitably reduce the air inflow of working gas argon gas, keep operating air pressure at 0.5-1.0Pa;
(5) open the substrate tumbler, set 8-10 rev/min, and open the substrate baffle plate;
(6) but on SOI covariant substrate first sputter one deck zinc oxide of growing in advance, underlayer temperature is 450-650 ℃, grows and shuts the substrate baffle plate after 1-3 minute;
(7) suitably reduce the air inflow of working gas argon gas, and lead to auxiliary reacting gas oxygen in main growth room, the flow-rate ratio of controlling argon gas and oxygen by gas flowmeter is 5: 1-9: 1, and the air pressure of always working is 0.5-1.0Pa;
(8) open the substrate baffle plate, but adopt the interchange RF sputtering method pre-the growth growing zinc oxide film on the SOI covariant substrate of ultra-thin zinc oxide film to be arranged, growth time is determined as required;
(9) close the interchange radio frequency operation power supply of zinc oxide target, stop the preparation growth of Zinc oxide film material, and block the plate washer of zinc oxide target;
(10) stop substrate and rotate, close working gas argon gas and auxiliary reacting gas oxygen, and open the slide valve between main growth room and vacuum pump fully, take out the vacuum of main growth room.
Step 7: the in-situ annealing of Zinc oxide film material is handled.Wherein, annealing temperature is 700-750 ℃, time 20-30 minute;
Step 8: the zinc oxide sample that will drop to room temperature is taken out, and finishes the preparation of Zinc oxide film material.
But the technical parameter of table 1:SOI covariant substrate
Table 2: but utilize magnetron sputtering apparatus on SOI covariant substrate, to prepare the main experiment parameter of developing zinc oxide epitaxial film materials
Realize the best way of invention:
1. realize the capital equipment of invention:
The cleaning equipment of magnetron sputtering apparatus, vacuum equipment (oil-sealed rotary pump, turbomolecular pump etc.), semiconductor substrate materials etc.;
2. the functional characteristics according to growth apparatus designs technology path of the invention process.
Embodiment 1:
At common Si (111) substrate, Si (100) but adopt identical dc reactive sputtering technology to carry out the preparation increment study of Zinc oxide film material on substrate and the SOI covariant substrate.Wherein, but the top ultra-thin silicon monocrystalline bed thickness of selected SOI covariant substrate is 30nm, and the thick middle silicon dioxide insulating layer is thick to be 500nm, and the Rutherford backscattering test result of this substrate is referring to Fig. 1.Distance setting between metallic zinc target and substrate is 5.5cm, the sputtering power of DC power supply work is controlled at about 45W, the flowrate proportioning of working gas argon gas and reacting gas oxygen is controlled at about 1: 4, and the air pressure of always working is about 1.0Pa, and substrate heating temperature is 350 ℃.Earlier 1 minute metallic zinc of pre-growth on the substrate with prevent substrate surface by after the reacting gas dioxygen oxidation that feeds, logical then reacting gas oxygen carried out the reactive sputtering developing zinc oxide 210 minutes.The back in-situ annealing 30 minutes under 750 ℃ high temperature that stops growing is waited to drop to room temperature and is taken out sample and carry out test analysis.Prepared zinc oxide films membrane sample has been carried out atomic force surface topography (AFM) and X-ray diffraction (XRD) test analysis, and test result is referring to Fig. 2, Fig. 3.
A, the b, the two-dimensional surface roughness (RMS) of three Z nO of c film sample in 1 * 1 μ m yardstick that are provided by atomic force surface topography (AFM) Measurement results of Fig. 2 are respectively 4.0nm, 2.9nm, 1.9nm.Show that the ZnO film sample surfaces on the SOI substrate is Paint Gloss smooth.ZnO film sample surfaces pattern on two common Si substrates one of the relatively poor possible cause that compares is the bigger internal stress of rete inner accumulated.
By X-ray diffraction (XRD) test result of Fig. 3 as can be seen, compare ZnO sample a on common Si (111) substrate and the ZnO sample b on common Si (100) substrate, 2 θ angle minimums (34.18 °) of ZnO (002) diffraction maximum of X-ray diffraction (XRD) test result of the ZnO sample c on the SOI substrate, and halfwidth (FWHM) is worth also minimum (0.303 °), and the ZnO that calculates (002) face interplanar distance d value is maximum (2.6211 but
), the value that provides X ray swing curve (XRC) halfwidth (FWHM) of its ZnO (002) diffraction maximum is 4.824 °.And 2 θ angles of Z nO (002) diffraction maximum of zinc oxide films membrane sample a, b on two kinds of common Si substrates are respectively 34.24 °, 34.22 °, and halfwidth (FWHM) is respectively 0.376 °, 0.368 °, and ZnO (002) face interplanar distance d value is respectively 2.6167
2.6207
And all can not provide X ray swing curve (XRC) halfwidth (FWHM) of smaller ZnO (002) diffraction maximum.Proved that further tensile residual stresses reduces in the ZnO film sample rete on the SOI substrate, and crystalline quality improves.
But above-mentioned experimental result explanation SOI covariant substrate has reasonable misfit strain coordinative role, adopt the tensile residual stresses of the zinc oxide films membrane sample of direct current sputtering method preparation growth to reduce on it, and crystalline quality improves, and surface topography is also better improved.
Embodiment 2:
At common Si (111) substrate, Si (100) but adopt identical interchange RF-reactively sputtered titanium technology to carry out the preparation increment study of Zinc oxide film material on substrate and the SOI covariant substrate.Wherein, but the top ultra-thin silicon monocrystalline bed thickness of selected SOI covariant substrate is 30nm, and the thick middle silicon dioxide insulating layer is thick to be 500nm, and the Rutherford backscattering test result of this substrate is referring to Fig. 1.Distance setting between zinc oxide target and substrate is 7.5cm, the sputtering power that exchanges radio-frequency power supply work is controlled at about 80W, the flowrate proportioning of working gas argon gas and assisted reaction gas oxygen is controlled at about 9: 1, and the air pressure of always working is about 0.5Pa, and substrate heating temperature is 500 ℃.First 2 minutes zinc oxide of pre-growth on substrate, with prevent substrate surface by after the assisted reaction gas dioxygen oxidation that feeds, logical then assisted reaction gas oxygen continued the sputter developing zinc oxide 180 minutes.The back in-situ annealing 30 minutes under 750 ℃ high temperature that stops growing is waited to drop to room temperature and is taken out sample and carry out test analysis.Prepared zinc oxide films membrane sample has been carried out atomic force surface topography (AFM) and X-ray diffraction (XRD) test analysis, and test result is referring to Fig. 4,5.
Atomic force surface topography (AFM) Measurement results by Fig. 4 provides a, b, the two-dimensional surface roughness (RMS) of three Z nO of c film sample in 1 * 1 μ m yardstick is respectively 9.1nm, 8.8nm, 7.0nm.Illustrate that the ZnO film sample on the SOI substrate has better smooth planar surface.One of relatively poor possible cause is the bigger internal stress of rete inner accumulated and the surface topography of two ZnO film sample a, b on the common Si substrate compares.
By X-ray diffraction (XRD) test result of Fig. 5 as can be seen, compare ZnO sample a on common Si (111) substrate and the ZnO sample b on common Si (100) substrate, 2 θ angle minimums (34.444 °) of ZnO (002) diffraction maximum of X-ray diffraction (XRD) test result of the ZnO sample c on the SOI substrate, and halfwidth (FWHM) is worth also minimum (0.3342 °), and the ZnO that calculates (002) face interplanar distance d value is maximum (2.60168 but
), the value that provides X ray swing curve (XRC) halfwidth (FWHM) of its ZnO (002) diffraction maximum is 3.366 °.And 2 θ angles of ZnO (002) diffraction maximum of the zinc oxide films membrane sample on two kinds of common Si substrates are respectively 34.420 °, 34.459 °, and halfwidth (FWHM) is respectively 0.3844 °, 0.3509 °, and ZnO (002) face interplanar distance d value is respectively 2.60320
2.60963
The a sample is not realized single preferred orientation growth, so can not provide X ray swing curve (XRC) halfwidth (FWHM) of ZnO (002) diffraction maximum, though the b sample has been realized single preferred orientation growth, X ray swing curve (XRC) halfwidth (FWHM) of ZnO (002) diffraction maximum that provides is bigger, is 4.209 °.These results have shown that further the interior tensile residual stresses of the ZnO film sample rete on the SOI substrate reduces, and crystalline quality improves.
Can prove that by above-mentioned experimental result but SOI covariant substrate has reasonable misfit strain coordinative role, adopt the tensile residual stresses of the zinc oxide films membrane sample that exchanges RF sputtering method preparation growth to reduce, and crystalline quality improves, and surface topography is also better improved.
Claims (7)
1. method for preparing Zinc oxide film material, but be meant a kind of SOI of utilization covariant substrate especially, adopt magnetron sputtering apparatus to prepare the method for growing zinc oxide film material, it is characterized in that, comprise the steps:
Step 1: select for use the top to have the SOI material of ultra-thin silicon single crystalline layer as the silicon based compliant substrate;
Step 2: with the sputtering target material primary growing room of magnetron sputtering device of packing into;
Step 3: the pre-sputter process in surface of carrying out sputtering target material;
Step 4: the main growth room of magnetron sputtering apparatus but the SOI covariant substrate that will clean is packed into;
Step 5: but carry out the heated baking degassing processing of SOI covariant substrate;
Step 6: the magnetically controlled sputter method preparation growth of Zinc oxide film material;
Step 7: the in-situ annealing of Zinc oxide film material is handled;
Step 8: the zinc oxide sample that will drop to room temperature is taken out, and finishes the preparation of Zinc oxide film material.
2. preparation Zinc oxide film material method according to claim 1 is characterized in that: wherein the SOI material described in the step 1 is that ultra-thin Si single crystalline layer, the centre of adopting the top of energetic oxygen ions method for implanting preparation to have 10-50nm thickness has the three-decker large scale SOI material that the insulating layer of silicon oxide and the bottom of 200-600nm thickness have (100) orientation silicon monocrystalline substrate.
3. preparation Zinc oxide film material method according to claim 1 is characterized in that: wherein the sputtering target material in the step 3 is a purity greater than 99.99% metallic zinc and zinc oxide material.
4. preparation Zinc oxide film material method according to claim 3 is characterized in that, metallic zinc target wherein is to adopt the dc reactive sputtering method to carry out the Zinc oxide film material preparation.
5. preparation Zinc oxide film material method according to claim 3 is characterized in that, zinc oxide target wherein is to adopt the interchange RF sputtering method to carry out the Zinc oxide film material preparation.
6. according to claim 1,3,4 described preparation Zinc oxide film material methods, it is characterized in that, wherein, distance between metallic zinc target and substrate is 5-7c m, the reactive sputtering power of DC power supply is 40-60W, the flowrate proportioning of working gas argon gas and reacting gas oxygen is 1: 4-1: 3, total work air pressure is 0.5-1.0Pa, underlayer temperature is 350-550 ℃, pre-growth time and growth time are respectively 1-3 minute and 180-210 minute, and at 700-750 ℃ of following in-situ annealing 20-30 minute.
7. according to claim 1,3,5 described preparation Zinc oxide film material methods, it is characterized in that, wherein, the distance of zinc oxide target and substrate is 6-8cm, the sputtering power that exchanges radio-frequency power supply is 80-100W, the flowrate proportioning of working gas argon gas and assisted reaction gas oxygen is 4: 1-9: 1, total work air pressure is 0.5-1.0Pa, underlayer temperature is 450-650 ℃, pre-growth time and growth time are respectively 1-3 minute and 180-210 minute, and at 700-750 ℃ of following in-situ annealing 20-30 minute.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100030727A CN100424825C (en) | 2006-02-08 | 2006-02-08 | Method for making the growth ZnO thin film material with the covariant underlay |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100030727A CN100424825C (en) | 2006-02-08 | 2006-02-08 | Method for making the growth ZnO thin film material with the covariant underlay |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101017776A CN101017776A (en) | 2007-08-15 |
| CN100424825C true CN100424825C (en) | 2008-10-08 |
Family
ID=38726675
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100030727A Expired - Fee Related CN100424825C (en) | 2006-02-08 | 2006-02-08 | Method for making the growth ZnO thin film material with the covariant underlay |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100424825C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9214563B2 (en) | 2009-09-24 | 2015-12-15 | Semiconductor Energy Laboratory Co., Ltd. | Oxide semiconductor film and semiconductor device |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102842672B (en) * | 2012-09-06 | 2016-01-20 | 电子科技大学 | Ferroelectric thin film/resilient coating/semiconductor integrated device and preparation method |
| CN112831766B (en) * | 2021-01-04 | 2022-04-01 | 南京佑天金属科技有限公司 | Method for preparing zirconium metal film on silicon substrate by utilizing magnetron sputtering and application |
| CN112939060B (en) * | 2021-02-05 | 2022-02-15 | 中国人民解放军战略支援部队航天系统部装备部装备保障队 | Zinc oxide nano material and preparation method and application thereof |
| CN114574961A (en) * | 2022-03-23 | 2022-06-03 | 广东省智能机器人研究院 | Zinc oxide film growth method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010008656A1 (en) * | 1994-01-27 | 2001-07-19 | Michael A. Tischler | Bulk single crystal gallium nitride and method of making same |
| US20050253136A1 (en) * | 2004-04-30 | 2005-11-17 | Sharp Laboratories Of America, Inc. | Electroluminescent device |
| CN1707752A (en) * | 2004-06-09 | 2005-12-14 | 中国科学院上海硅酸盐研究所 | Spray pyrolyzation processing method for nitride mixing hole type zinc oxide thin film material |
-
2006
- 2006-02-08 CN CNB2006100030727A patent/CN100424825C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010008656A1 (en) * | 1994-01-27 | 2001-07-19 | Michael A. Tischler | Bulk single crystal gallium nitride and method of making same |
| US20050253136A1 (en) * | 2004-04-30 | 2005-11-17 | Sharp Laboratories Of America, Inc. | Electroluminescent device |
| CN1707752A (en) * | 2004-06-09 | 2005-12-14 | 中国科学院上海硅酸盐研究所 | Spray pyrolyzation processing method for nitride mixing hole type zinc oxide thin film material |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9214563B2 (en) | 2009-09-24 | 2015-12-15 | Semiconductor Energy Laboratory Co., Ltd. | Oxide semiconductor film and semiconductor device |
| US9318617B2 (en) | 2009-09-24 | 2016-04-19 | Semiconductor Energy Laboratory Co., Ltd. | Method for manufacturing a semiconductor device |
| US9853167B2 (en) | 2009-09-24 | 2017-12-26 | Semiconductor Energy Laboratory Co., Ltd. | Oxide semiconductor film and semiconductor device |
| US10418491B2 (en) | 2009-09-24 | 2019-09-17 | Semiconductor Energy Laboratory Co., Ltd. | Oxide semiconductor film and semiconductor device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101017776A (en) | 2007-08-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103915537B (en) | Growth method of compound semiconductor epitaxial layer on silicon substrate and device structure with epitaxial layer | |
| CN100424825C (en) | Method for making the growth ZnO thin film material with the covariant underlay | |
| CN107083540B (en) | A kind of gallium nitride base film and preparation method thereof on flexible polyimide substrate | |
| US20110315074A1 (en) | Single-crystal diamond growth base material and method for manufacturing single-crystal diamond substrate | |
| CN102251216B (en) | Method for preparing tungsten-doped vanadium oxide film | |
| CN107354428A (en) | The aluminum nitride buffer layer and active layer formed by physical vapour deposition (PVD) | |
| CN102623521A (en) | Method for preparing cuprous oxide film | |
| US20110089415A1 (en) | Epitaxial growth of single crystalline mgo on germanium | |
| CN102002668B (en) | Polysilicon film low-temperature physical vapor deposition device and method thereof | |
| CN101514440A (en) | Method for preparation of indium oxide transparent film with high electron mobility | |
| JPH04266019A (en) | Film formation | |
| CN105731825A (en) | Method for preparing aluminum nitride thin film by utilizing graphene glass at low cost and large area | |
| CN116705594B (en) | Thin film semiconductor and diamond composite substrate and manufacturing method thereof | |
| CN101325227A (en) | Method for preparing ZnO/nanometer diamond coplane grid ultraviolet light detector | |
| CN110257798A (en) | A kind of ICP-CVD prepares the deposition method of amorphous carbon film | |
| CN110629184B (en) | Method for directly growing two-dimensional hexagonal boron nitride on dielectric substrate | |
| CN101017864A (en) | Silicon base covariant underlay with the ultrathin carbon silicon middle layer and its preparing method | |
| CN101017830A (en) | SOI compound covariant layer underlay with the metal Hafnium middle layer | |
| CN108220897B (en) | The method of magnetron sputtering low temperature preparation vanadium dioxide film | |
| CN113862622A (en) | Preparation method of metal compound film | |
| CN104790029B (en) | A kind of method for preparing SnO epitaxial films | |
| US20100062585A1 (en) | Method for forming silicon thin film | |
| CN108060458B (en) | A kind of preparation facilities and method of nonpolarity indium nitride nano-crystal film | |
| Kong et al. | Characterization of single-crystalline In2O3 films deposited on y-stabilized ZrO2 (1 0 0) substrates by MOCVD | |
| CN102877035A (en) | Method for preparing silicon-based germanium film with low-temperature buffer layer by means of cyclic stress modulation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20081008 |