CN1203558C - Transparent n-type zinc oxide/p-type diamond film heterojunction and its preparation - Google Patents
Transparent n-type zinc oxide/p-type diamond film heterojunction and its preparation Download PDFInfo
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- CN1203558C CN1203558C CNB021329028A CN02132902A CN1203558C CN 1203558 C CN1203558 C CN 1203558C CN B021329028 A CNB021329028 A CN B021329028A CN 02132902 A CN02132902 A CN 02132902A CN 1203558 C CN1203558 C CN 1203558C
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Abstract
The present invention relates to a transparent n-type zinc oxide/p-type diamond film heterojunction and a preparing method thereof. The transparent n-type zinc oxide/p-type diamond film heterojunction belongs to a transparent p-n junction. The transparent n-type zinc oxide/p-type diamond film heterojunction adopts a diamond single crystal as a substrate (5). The technological process comprises the steps: (10), cleaning the substrate (5); (11), depositing a p-type diamond single crystal film; (12), chemically treating the p-type diamond single crystal film; (13), making ohmic electrodes for the diamond single crystal film; (14), selectively depositing an n-type zinc oxide polycrystal film (3); (15), making an ohmic electrode for the n-type zinc oxide polycrystal film (3). A boron source is put in the process of depositing the p-type diamond single crystal film (1); the ohmic electrodes (2) of the diamond single crystal film are a titanium film, a molybdenum film and a gold film orderly deposited; the ohmic electrode (4) of the n-type zinc oxide polycrystal film (3) is a gold film. The preparing method of the present invention has simple preparing process and easy realization; the transparent n-type zinc oxide/p-type diamond film heterojunction of the present invention has the characteristics of favorable volt-ampere property, optical transparency, high temperature resistance, favorable ohmic contact performance of the electrodes, and firm ohmic contact of the electrodes.
Description
Technical field
The invention belongs to the process of a kind of transparent knot and preparation thereof, be particularly related to the heterojunction that n-type zinc oxide polycrystal film/P-type single crystal diamond diaphragm constitutes, and the preparation of the homoepitaxy of single crystal diamond diaphragm and ohmic contact thereof, the deposition of zinc oxide and the preparation of ohmic contact thereof.
Background technology
The background technology the most similar to the present invention is U.S. Patent application, and publication number is US 5334855A.This patent application discloses a kind of light-emitting diode, by N type ZnO:Zn polycrystal layer, boron doped P type diamond multicrystal layer and constitute with Zn polycrystal layer, the contacted contact layer of P type diamond multicrystal layer respectively.
In the background technology, because boron doped P type diamond multicrystal layer is polycrystalline, the prepared p-n heterojunction that goes out is opaque, therefore can not be applied on the opto-electronic device widely.Background technology does not relate to the electrode and the manufacture method of this light-emitting diode substantially.Common practise is routinely selected electrode material, and the electrode that makes this heterojunction will prepare firm ohmic contact is difficult.
Summary of the invention
Because diamond film has good electricity, optical characteristics and good heat conduction, insulation characterisitic, therefore can prepare multiple electronics, opto-electronic device and in semiconductor integrated circuit, make heat sink material and insulating material with it.Yet the n-type diamond that is suitable for preparing semiconductor device is difficult to obtain, and this has just limited the application of diamond film device greatly.On the other hand, zinc oxide is applied on the opto-electronic device widely as a kind of transparent oxide.Its outstanding characteristic is that its characteristic electron passes through the n-N-type semiconductor N to metal from insulator by changing oxygen, the zinc ratio in the zinc oxide.Though zinc oxide has very wide conduction scope, its application is limited only within on metal electrode and the optical transparence.For example, transparency electrode on the flat-panel monitor and solar cell.Because it is difficult unusually that the p-type of zinc oxide mixes, so only the transparent p-n junction that is made of zinc oxide is not reported.
The problem to be solved in the present invention is exactly to utilize the transparent characteristic of diamond single crystal and good electricity, optical characteristics and good heat conduction, the insulation characterisitic of diamond thin, the characteristics that P-type single crystal diamond diaphragm makes easily, utilizing zinc oxide is a kind of transparent oxide, the characteristics that n-type ZnO makes are easily prepared the heterojunction that transparent n-type zinc oxide polycrystal film/P-type single crystal diamond diaphragm constitutes.Not only the preparation technology of heterojunction simply is easy to realize, and n-type zinc oxide polycrystal film/P-type single crystal diamond diaphragm heterojunction has good volt-ampere characteristic, optical transparence and high temperature resistance characteristic, and the ohm contact performance of electrode is good and firm.
Transparent n-type zinc oxide polycrystal film of the present invention/p-type single crystal diamond diaphragm heterojunction is made of the Ohmic electrode of the Ohmic electrode of p-type single crystal diamond diaphragm, diamond thin, n-type zinc oxide polycrystal film, zinc-oxide film; P-type single crystal diamond diaphragm is produced on the diamond single crystal substrate; The Ohmic electrode of diamond thin and n-type zinc oxide polycrystal film are isolated mutually and are produced on the p-type single crystal diamond diaphragm; The Ohmic electrode that zinc-oxide film is arranged above the n-type zinc oxide polycrystal film; The Ohmic electrode of said diamond thin is the multilayer film of titanium, molybdenum, gold, and the Ohmic electrode of zinc-oxide film is golden film.
The thickness of p-type single crystal diamond diaphragm is 500～1500nm; The thickness of n-type zinc oxide polycrystal film is 200～500nm; The thickness of the Ohmic electrode of diamond thin is 100～1000nm, and the thickness of the Ohmic electrode of zinc-oxide film is 100～600nm.
Fig. 1 provides the structural representation of n-type zinc oxide polycrystal film of the present invention/p-type single crystal diamond diaphragm heterojunction.Among Fig. 1, the 1st, p-type single crystal diamond diaphragm, the 2nd, the Ohmic electrode of diamond thin, the 3rd, n-type zinc oxide polycrystal film, the 4th, the Ohmic electrode of zinc-oxide film, the 5th, diamond single crystal substrate.The Ohmic electrode 2 of diamond thin is isolated on the p-type that the is produced on single crystal diamond diaphragm 1 that is not connected by the pattern of design mutually with n-type zinc oxide polycrystal film 3.
The preparation method of transparent n-type zinc oxide/p-type diamond film heterojunction of the present invention, be to be substrate with the diamond single crystal, technical process comprises that the Ohmic electrode of chemical treatment, the diamond thin of deposition, the p-type single crystal diamond diaphragm of cleaning, the p-type single crystal diamond diaphragm of substrate is made, the making of the Ohmic electrode of the selective deposition of n-type zinc oxide polycrystal film, zinc-oxide film.
The cleaning of said substrate is that diamond single crystal substrate 5 usefulness ethanol and acetone mixed solution are carried out ultrasonic cleaning, carries out chemical cleaning with nitric acid and hydrochloric acid mixed solution then, dries with washed with de-ionized water and with infrared lamp at last;
The deposition of said p-type single crystal diamond diaphragm is on the diamond single crystal substrate 5 that cleaned, with hot-wire chemical gas-phase deposition method epitaxial growth P-type single crystal diamond diaphragm 1, to place the boron source during deposition;
The chemical treatment of said p-type single crystal diamond diaphragm is that the saturated solution with the chromium trioxide and the concentrated sulfuric acid carries out chemical treatment 3～10 minutes under 150～180 ℃ condition, then sample is immersed in the mixed solution of 60～80 ℃ hydrogen peroxide and ammoniacal liquor, at last with deionized water rinsing and oven dry;
The Ohmic electrode of said diamond thin is made: with the method for AC magnetic controlled sputter optionally sequential aggradation titanium, molybdenum, gold thin film, form the Ohmic electrode 2 of the diamond thin of multilayer film, again sample was annealed 0.5～3 hour under 400～420 ℃ the condition in air;
The selective deposition of said n-type zinc oxide polycrystal film is to use magnetically controlled sputter method, at the deposition n-type zinc oxide polycrystal film 3 of p-type single crystal diamond diaphragm 1 surface selectivity;
The making of the Ohmic electrode of said zinc-oxide film is with magnetically controlled sputter method golden film on the deposition of n-type zinc oxide polycrystal film 3 surface selectivities, to form the Ohmic electrode 4 of zinc-oxide film.
Aforesaid optionally sequential aggradation titanium, molybdenum, gold thin film, optionally deposit n-type zinc oxide polycrystal film 3 or deposited gold film optionally, the process of its selective deposition is accordingly: at first, be carved into figure on the surface of p-type single crystal diamond diaphragm 1 or n-type zinc oxide polycrystal film 3 with photoresist, in this figure, need the photoresist at the position of deposit multilayer metal film, zinc oxide polycrystal film or golden film to be etched away; Secondly, deposition goes up the Ohmic electrode 2 and the n-type zinc oxide polycrystal film 3 of titanium, molybdenum, the film formed diamond thin of golden multilayer or deposits the Ohmic electrode 4 of going up golden film formed zinc-oxide film respectively; Once more, the sodium hydroxide solution with 0.5% etches away photoresist, uses the sodium hydroxide solution better effects if of heat, and in this process, the metal multilayer film on the photoresist, zinc oxide polycrystal film or golden film are removed simultaneously, have so just realized selective growth.
Fig. 2 provides the preparation method's of transparent n-type zinc oxide/p-type diamond film heterojunction of the present invention process flow diagram.Can know the technical process of finding out preparation of image by Fig. 2.Among Fig. 2,10 is the cleaning of substrate, and 11 is the deposition of p-type single crystal diamond diaphragm, 12 is the chemical treatment of p-type single crystal diamond diaphragm, 13 is the Ohmic electrode making of diamond thin, and 14 is the selective deposition of n-type zinc oxide polycrystal film, and 15 is the making of the Ohmic electrode of zinc-oxide film.
The present invention compares with background technology, p-type and n-N-type semiconductor N material all are easier to obtain, make the preparation technology of heterojunction simply be easy to realize, and n-type zinc oxide polycrystal film/P-type single crystal diamond diaphragm heterojunction have good volt-ampere characteristic, optical transparence.And the adamantine energy gap of n-type is big (5.4eV), so have the high temperature resistance characteristic.Owing to selected suitable metal and technology to make electrode, made the ohm contact performance of electrode good and firm.
Fig. 3 provides the volt-ampere characteristic between p-type single crystal diamond diaphragm 1 and the metallic multilayer membrane electrode 2, and it is a straight line as can be seen, thereby contacting between proof titanium/molybdenum/golden multilayer film and the single crystal diamond diaphragm is ohmic contact.
Fig. 4 has provided the volt-ampere characteristic between n-type zinc oxide polycrystal film 3 and the gold film electrode 4, and it is a class straight line as can be seen, thereby proves contacting away from Schottky contacts between golden film and the n-type zinc oxide polycrystal film 3, and approaches ohmic contact.
Fig. 5 has provided the volt-ampere characteristic of heterojunction of the present invention, and as can be seen from Figure 5 this heterojunction has rectification characteristic, and its threshold value is 0.5V, and commutating ratio is about 100, and the forward maximum current is 5mA.
Fig. 6 has provided the optical transparence of this heterojunction, and as can be seen from the figure its optical transmittance between 500-700nm is 50-70%.
Description of drawings
Fig. 1 is transparent n-type zinc oxide of the present invention/p-type diamond film heterojunction structural representation.
Fig. 2 is preparation technology's schematic flow sheet of transparent n-type zinc oxide/p-type diamond film heterojunction of the present invention.
Fig. 3 is the volt-ampere characteristic between p-type single crystal diamond diaphragm of the present invention and the metallic multilayer membrane electrode.
Fig. 4 is the volt-ampere characteristic between n-type zinc oxide polycrystal film of the present invention and the gold film electrode.
Fig. 5 is the volt-ampere characteristic of transparent n-type zinc oxide/p-type diamond film heterojunction of the present invention.
Fig. 6 is the optical transparence of transparent n-type zinc oxide/p-type diamond film heterojunction of the present invention.
Embodiment
The deposition of embodiment 1 p-type single crystal diamond diaphragm
When preparation p-type single crystal diamond diaphragm, with hot-wire chemical gas-phase deposition method epitaxial growth diamond thin, place the boron source in the reative cell, mix to carry out boron.The deposition 11 of p-type single crystal diamond diaphragm must be carried out under the following conditions for this reason: growth air pressure is 1000-3000Pa, underlayer temperature is 800-1000 ℃, the volume ratio of methane and hydrogen is 1/100-3/100, growth time is 1-3 hour, and the thickness of epitaxially grown single crystal diamond diaphragm is about 500-1500nm.
Be described below as a special case.Experiment parameter is: air pressure 1000Pa, and 850 ℃ of underlayer temperatures, the volume ratio 1/100 of methane and hydrogen, sedimentation time 1 hour, having obtained thickness is the better p-type of the quality diamond thin 1 of 500nm.
The cleaning of embodiment 2 substrates
The backing material of preparation heterojunction can be amber single-crystal diamond.
Before deposition p-type diamond thin, earlier the diamond single crystal substrate is carried out ultrasonic cleaning with degrease with 1: 1 ethanol and acetone mixed solution, use 1: 3 nitric acid and hydrochloric acid mixed solution to carry out chemical cleaning to remove the metal ion of diamond surface then, this sample is dried with washed with de-ionized water and with infrared lamp at last.
The Ohmic electrode of embodiment 3 diamond thins is made
Optionally titanium deposition, molybdenum, golden multilayer film are made the Ohmic electrode 2 of diamond thin with the method for AC magnetic controlled sputter.Said multilayer film is exactly the trilamellar membrane by titanium molybdenum gold order.At last, can be with sample annealing 1 hour under 410 ℃ the condition in air, so that ohm alloy merges and firmly.The thickness of titanium, molybdenum, golden multilayer film can be selected titanium (50nm)/molybdenum (100nm)/gold (300nm).
The selective deposition of embodiment 4 n-type zinc oxide polycrystal films
With the deposition n-type zinc oxide polycrystal film 3 of magnetically controlled sputter method at p-type single crystal diamond diaphragm 1 surface selectivity, its technological parameter is as follows: the diameter of zinc oxide target is 50mm, and the distance of target and substrate is 45-90mm, and the power density of sputter is 3-6W/cm
2, back of the body end vacuum is 10
-4Pa, sputter gas are the mist of oxygen and argon gas, and gas volume is than 5/20-10/20, and sputtering pressure is 0.8-2.8Pa, and the thickness of Zinc oxide film is about 200-500nm.
Be described below as a special case.Selecting the distance of target and substrate is 45mm, and the power density of sputter is 3W/cm
2, gas volume is than 10/20, sputtering pressure is 1.0Pa, obtain quality preferably thickness be the ZnO film of 200nm.
Claims (3)
1, a kind of transparent n-type zinc oxide/p-type diamond film heterojunction is made of the Ohmic electrode (4) of the Ohmic electrode (2) of diamond thin, n-type zinc oxide polycrystal film (3), zinc-oxide film; The Ohmic electrode (4) of zinc-oxide film is arranged above the n-type zinc oxide polycrystal film (3), it is characterized in that, structure also has p-type single crystal diamond diaphragm (1), and p-type single crystal diamond diaphragm (1) is produced on the diamond single crystal substrate (5); Ohmic electrode of diamond thin (2) and n-type zinc oxide polycrystal film (3) isolation mutually are produced on the p-type single crystal diamond diaphragm (1); The Ohmic electrode of said diamond thin (2) is the multilayer film of titanium, molybdenum, gold, and the Ohmic electrode of zinc-oxide film (4) is golden film.
2, according to the described transparent n-type zinc oxide of claim 1/p-type diamond film heterojunction, it is characterized in that the thickness of p-type single crystal diamond diaphragm (1) is 500～1500nm; The thickness of n-type zinc oxide polycrystal film (3) is 200～500nm; The thickness of the Ohmic electrode of diamond thin (2) is 100～1000nm, and the thickness of the Ohmic electrode of zinc-oxide film (4) is 100～600nm.
3, a kind of preparation method of transparent n-type zinc oxide/p-type diamond film heterojunction, technical process comprise that the cleaning (10) of substrate, the deposition (11) of p-type single crystal diamond diaphragm, the chemical treatment (12) of p-type single crystal diamond diaphragm, the Ohmic electrode of diamond thin make the making (15) of the Ohmic electrode of the selective deposition (14) of (13), n-type zinc oxide polycrystal film, zinc-oxide film; It is characterized in that, be substrate with the diamond single crystal;
The deposition (11) of said p-type single crystal diamond diaphragm is on the diamond single crystal substrate (5) that cleaned, with hot-wire chemical gas-phase deposition method epitaxial growth P-type single crystal diamond diaphragm (1), to place the boron source during deposition; The deposition (11) of p-type single crystal diamond diaphragm is carried out under the following conditions: growth air pressure is 1000-3000Pa, underlayer temperature is 800-1000 ℃, the volume ratio of methane and hydrogen is 1/100-3/100, growth time is 1-3 hour, and the thickness of epitaxially grown single crystal diamond diaphragm is 500-1500nm;
The Ohmic electrode of said diamond thin is made (13): with the method for AC magnetic controlled sputter optionally sequential aggradation titanium, molybdenum, gold thin film, form the Ohmic electrode (2) of the diamond thin of multilayer film, in air, annealed under 400～420 ℃ the condition 0.5～3 hour again;
The selective deposition (14) of said n-type zinc oxide polycrystal film is to use magnetically controlled sputter method, at the deposition n-type zinc oxide polycrystal film (3) of p-type single crystal diamond diaphragm (1) surface selectivity;
The making of the Ohmic electrode of said zinc-oxide film (15) is with magnetically controlled sputter method golden film on the deposition of n-type zinc oxide polycrystal film (3) surface selectivity, to form the Ohmic electrode (4) of zinc-oxide film.
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| CNB021329028A CN1203558C (en) | 2002-09-08 | 2002-09-08 | Transparent n-type zinc oxide/p-type diamond film heterojunction and its preparation |
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| CNB021329028A CN1203558C (en) | 2002-09-08 | 2002-09-08 | Transparent n-type zinc oxide/p-type diamond film heterojunction and its preparation |
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| CN1203558C true CN1203558C (en) | 2005-05-25 |
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| CN104810428A (en) * | 2014-01-25 | 2015-07-29 | 泉州市博泰半导体科技有限公司 | Method for processing bonding layer during manufacture of silicon-based heterojunction cell |
| CN108417618B (en) * | 2018-02-09 | 2021-08-27 | 沈阳工程学院 | Si substrate heterostructure device and preparation method thereof |
| CN110428923B (en) * | 2019-08-09 | 2021-06-29 | 哈尔滨工业大学 | Diamond Schottky isotope battery adopting zinc oxide layer to improve performance and preparation method thereof |
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