CN101868862A - Photodetector for ultraviolet and method for manufacturing the photodetector - Google Patents
Photodetector for ultraviolet and method for manufacturing the photodetector Download PDFInfo
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- CN101868862A CN101868862A CN200880117234A CN200880117234A CN101868862A CN 101868862 A CN101868862 A CN 101868862A CN 200880117234 A CN200880117234 A CN 200880117234A CN 200880117234 A CN200880117234 A CN 200880117234A CN 101868862 A CN101868862 A CN 101868862A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J1/00—Photometry, e.g. photographic exposure meter
- G01J1/42—Photometry, e.g. photographic exposure meter using electric radiation detectors
- G01J1/429—Photometry, e.g. photographic exposure meter using electric radiation detectors applied to measurement of ultraviolet light
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
- H01L31/10—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors characterised by potential barriers, e.g. phototransistors
- H01L31/101—Devices sensitive to infrared, visible or ultraviolet radiation
- H01L31/102—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier
- H01L31/108—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier the potential barrier being of the Schottky type
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- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Light Receiving Elements (AREA)
Abstract
Provided is a low-cost photodetector for ultraviolet. The photodetector has excellent durability and does not require thin film deposition. The photodetector for ultraviolet is provided with a gallium oxide single crystal substrate; a first electrode, which is formed on the front surface of the gallium oxide single crystal substrate, provided with a light receiving surface and is brought into Schottky contact with the gallium oxide single crystal substrate; and a second electrode, which is formed on the rear surface of the gallium oxide single crystal substrate and brought into ohmic contact with the gallium oxide single crystal substrate. A current is permitted to flow between the first electrode and the second electrode through the gallium oxide single crystal substrate, corresponding to ultraviolet received by the light receiving surface.
Description
Technical field
The present invention relates to a kind of ultraviolet ray photodetector and manufacture method thereof, even if this ultraviolet ray with photodetector in daytime that has sunlight and the outdoor influence that also can not be subjected to sunray, can be in high sensitivity the only following ultraviolet ray of wavelength 280nm of sending such as flame detection, harmful substance.
Background technology
Sunlight blind (Solar-blind) type UV sensor (ultraviolet ray photodetector) expectation is as the easy flame sensor of small-sized solid-state components type, and expectation is used for the Sensor section of flame detecting equipment, cigarette (smoking) detecting devices, and the automatic control of the combustion flame of home-use combustion apparatus and industrial furnace is with in the sensing.
Further, also can consider to be used as the transducer that the ultraviolet surveillance device in the ultraviolet exposure apparatus according of using is used in the making of the super LSI of the next generation (large scale integrated circuit).
So far, as the transducer that only detects the deep UV below the wavelength 280nm (ultraviolet ray use photodetector), known have a photoelectric tube.This photoelectric tube is practical as the transducer that lighting of flame detection extinguished (flicker), is mainly used in the flame sensor of the automatic control usefulness of large-scale burners such as industrial furnace.But, exist the high problem of short cost of life-span with the transducer of photocell detection deep UV.
Relative therewith, with regard to as small-sized easy flame sensor and by for the transducer of the solid-state components type expected, can expect that wide band gap semiconducter is a GaN class III group-III nitride semiconductor, study the application (for example, please refer to following non-patent literature 1) of AlGaN film.In addition, also discussing the UV sensor (for example, please refer to following non-patent literature 2) of using diamond semiconductor.
And, can consider to use gallium oxide single crystal at the electrode of this UV sensor.
Because gallium oxide single crystal is water white, and band gap (bandgap: band gap) be 4.8eV, bigger, so discussing the optical material of ultraviolet region, light-emitting component such as LED and LD, all application such as grid material of the semiconductor usefulness substrate of light receiving elements such as UV sensor and oxidic transparent electric conductor, high-temperature oxygen body sensor, field-effect transistor (FET), FET.
When this gallium oxide single crystal is used as device, need electrode structure.Even if use the electrode material that Al, Pt, W etc. are generally discussing so far, also do not obtain good Ohmic contact.On the other hand, for example in following non-patent literature 3 and 4, proposed Ga
2O
3With the report of Au as electrode.In addition, in following patent documentation 1, propose as the combination of electrode with Au and Ti etc.
Non-patent literature 1: open country light: " GaN system be subjected to the scorching セ Application サ one ヘ ying of light sub-prime fire with (to the application of the flame sensor of GaN class light receiving element) ", ying is with No. 7 (1999) pp.0805-0809 of physics (Applied Physics) the 68th volume
Non-patent literature 2: go out Kang Fu for a short time: " グ イ ヤ モ Application De ultraviolet Line セ Application サ one (diamond UV sensor) ", ま て り あ (Materia: No. 4 (2007) pp.272-277 of the 46th volume material)
Non-patent literature 3:N.Ueda et al, " Synthesis and control of conductivity ofultraviolet transmitting β-Ga
2O
3Single crystals ", Appl.Phys.Lett.70 (26), (1997) pp.3561-3563
Non-patent literature 4:E.g.Villora et al, " Infrared reflectance and electricalconductivity of β-Ga
2O
3", Phys.stat.sol (a) 193, (2002) pp.187-195
Patent documentation 1: TOHKEMY 2004-56098 communique
, the transducer in the above-mentioned non-patent literature 1 be on substrate epitaxial growth and film, as the AlGaN of the mixed crystal of GaN and AlN, be positioned at the situation that is difficult to carry out high-quality film growth, in the manufacture method of practicality, have a lot of problems.
On the other hand, about the diamond film in the non-patent literature 2, when using cvd diamond substrate to carry out isoepitaxial growth (homoepitaxial growth), though the diamond film of growing high quality, but exist in the case, owing to substrate price height makes the such problem of cost rising.In addition, also there is the little such problem of sensitivity to the line spectrum 254nm of the Cooper-Hewitt lamp that is used for sterilization etc.
And, even if in above-mentioned document about the electrode structure of gallium oxide, the conductivity of the expectation that also not accomplished device is essential.
Use the device of film like this, because the film of growth is exerted one's influence to substrate,, make the technical process easy so wish to carry out device filmily by not using, and can make at an easy rate, wish the device of this transducer (ultraviolet ray photodetector).
Summary of the invention
It is superior to the purpose of this invention is to provide the durability aspect, does not need film growth, cheaply the ultraviolet ray photodetector.
In order to address the above problem, ultraviolet ray of the present invention comprises with photodetector: gallium oxide single crystal (single crystal) substrate; First electrode, the surface that it is formed at above-mentioned gallium oxide single crystal substrate has light receiving surface, and constitutes Schottky contacts with above-mentioned gallium oxide single crystal substrate; With second electrode, it is formed at the back side of above-mentioned gallium oxide single crystal substrate, constitute ohmic contact with above-mentioned gallium oxide single crystal substrate, and and the ultraviolet ray that receives by above-mentioned light receiving surface correspondingly between this second electrode and above-mentioned first electrode through above-mentioned gallium oxide single crystal flow of substrates overcurrent.
In addition, ultraviolet ray of the present invention comprises with photodetector: the gallium oxide single crystal substrate, and it is formed with low carrier density layer or insulating barrier on the surface; First electrode, above-mentioned low carrier density layer or surface of insulating layer that it is arranged at above-mentioned gallium oxide single crystal substrate have light receiving surface; With second electrode, it is arranged on the above-mentioned low carrier density layer or surface of insulating layer of above-mentioned gallium oxide single crystal substrate, and correspondingly crosses (flowing) electric current through above-mentioned gallium oxide single crystal flow of substrates between this second electrode and above-mentioned first electrode by the ultraviolet ray that above-mentioned light receiving surface receives.
In addition, the invention provides a kind of manufacture method of using the ultraviolet ray of gallium oxide single crystal substrate manufacture with photodetector, this manufacture method comprises: above-mentioned gallium oxide single crystal substrate is carried out pre-treatment (step), the surface of the above-mentioned gallium oxide single crystal real estate after finishing above-mentioned pre-treatment forms first electrode that constitutes Schottky contacts with above-mentioned gallium oxide single crystal substrate, and form with above-mentioned gallium oxide single crystal substrate at the back side of above-mentioned gallium oxide single crystal substrate and to constitute ohmic contact, and between self and above-mentioned first electrode through second electrode of above-mentioned gallium oxide single crystal flow of substrates overcurrent (step).
In addition, the invention provides a kind of manufacture method of using the ultraviolet ray of gallium oxide single crystal substrate manufacture with photodetector, this manufacture method comprises: form low carrier density layer or insulating barrier (step) on the surface of above-mentioned gallium oxide single crystal substrate, the low carrier density layer of above-mentioned gallium oxide single crystal substrate or surface of insulating layer form first electrode with light receiving surface and and the ultraviolet ray that receives by above-mentioned light receiving surface correspondingly between self and above-mentioned first electrode through second electrode of above-mentioned gallium oxide single crystal flow of substrates overcurrent (step).
In addition, ultraviolet ray of the present invention comprises with the manufacture method of photodetector: when when gallium oxide single crystal forms Ohmic electrode, evaporation Ti after plasma irradiating is carried out on the surface afterwards, forms the electrode that evaporation has Au/Ti structure, Pt/Ti structure or the Al/Ti structure of Au, Pt or Al.
In addition, ultraviolet ray of the present invention is with the manufacture method of photodetector, when when gallium oxide single crystal forms Ohmic electrode, evaporation Ti after plasma irradiating is carried out on the surface, afterwards, form the electrode that evaporation has Au/Ti structure, Pt/Ti structure or the Al/Ti structure of Au, Pt or Al, obtain thus.
Description of drawings
Fig. 1 is the Ga when changing heat treatment temperature
2O
3The AFM picture on monocrystal substrate surface.
Fig. 2 is the figure of the IV characteristic after the expression heat treatment in 3 hours.
Fig. 3 is the figure of the IV characteristic after the expression heat treatment in 6 hours.
Fig. 4 is to use Ga
2O
3The side view of the vertical photodetector of monocrystalline.
Fig. 5 is the process chart of the production process of expression photodetector.
Fig. 6 is the figure of expression photodetector electrode configuration.
Fig. 7 is the figure of the current-voltage characteristic of expression photodetector.
Fig. 8 is the figure that expression is radiated at the electric power of each wavelength on the light receiving surface.
Fig. 9 is the figure of expression spectrum analysis (beam split) sensory characteristic.
Figure 10 is the figure of expression spectrum analysis sensory characteristic.
Figure 11 is the key diagram of the work of expression execution mode 1.
Figure 12 is the key diagram of the work of expression execution mode 2.
Embodiment
Below, use the description of drawings embodiments of the present invention.
Execution mode 1
Below, embodiments of the present invention are described.1 pair of following situation of present embodiment describes: for respect to gallium oxide (Ga
2O
3) monocrystalline acquisition ohmic contact, perhaps in order to improve characteristic as the Au/Ti vapor-deposited film of the electrode material that can reduce contact resistance, heat treatment and pre-treatment condition by the monocrystalline before the investigation evaporation, use oxygen atmosphere, 1100 ℃, the heat treatment more than 3 hours and plasma irradiating in the lump, improve the IV characteristic of Au/Ti vapor-deposited film.
In order to select and Ga
2O
3Monocrystalline constitutes the material of ohmic contact, needs work function to equate with gallium oxide or below gallium oxide.The work function of gallium oxide is about 6eV, and Au, Ti are 4eV, and is littler than the gallium oxide.At first, the inventor makes Ga in order to carry out crystal growth and other application
2O
3The surface is with atomic level (level: rank) planarization.This passes through the Ga after the crystal formation
2O
3Anneal and obtain confirming.
Just with respect to Ga
2O
3The ohmic contact of monocrystalline, Au/Ti is satisfactory.Specifically, with Ga
2O
3Monocrystalline is a substrate, and behind the Ti of evaporation 30～60nm, secondly the Au of evaporation 150～250nm has made electrode at first thereon.Measure I-E characteristic, the result can access ohm property, and this is well-known.Annealing (annealing) condition be in oxygen atmosphere at 1100 ℃, carry out more than 3 hours.Can realize being formed with the flat surfaces of the atomic level of ladder (step), step (terrace) structure by this processing.
Here, the present inventor finds, in order further to reduce Ga
2O
3The resistance value on surface obtains more good Ohmic contact, by to the Ga after the crystal formation
2O
3Anneal, further plasma irradiating is carried out on the surface and generate defective, the result is to utilize the carrier electrons that produces can improve conductivity.
Annealing conditions is, in oxygen atmosphere, 1100 ℃ carry out more than 3 hours.By this processing, can form ladder, ledge structure from the teeth outwards, realize excellent contact.
The Ga of (600 ℃～1100 ℃) when Fig. 1 represents to change heat treatment temperature
2O
3The AFM on monocrystal substrate surface (Atomic Force Microscopy: atomic force microscope) as.Atmosphere is oxygen, and the time is 3 hours.Before this, as the pre-treatment of substrate, after carrying out organic cleaning, carry out 15 minutes processing and use H with HF5%
2SO
4: H
2O
2: H
2O=4: mixed liquor carried out 5 minutes processing in 1: 1.
From the result of Fig. 1 as seen, when temperature is 1100 ℃, observe clearly ladder, ledge structure.Think,, when the electrode evaporation material, can realize excellent contact by carrying out such heat treatment.Here, the present inventor finds to pass through at Ga
2O
3Irradiation plasma and generate defective on the surface so utilize the energy level of the defective that is produced, reduces contact resistance, can access more the characteristic as ohmic contact.
Then, to the Ga after the heat treatment
2O
3Monocrystal substrate carries out plasma irradiating as the processing before the evaporation.The purpose of plasma irradiating is to make forcibly to generate defective, improves electrical conductivity.
Specifically, utilize residual gas to produce the plasma of glow discharge to the specimen surface irradiation.Irradiation time is 30 minutes, and ionic current is hundreds of μ A.
Like this, to the Ga after the crystal formation
2O
3After heat-treating, plasma irradiating is carried out on the surface, afterwards, install electrode.As electrode material, preferably behind the Ti of about 50nm, evaporation 150～250nm is the Au of about 200nm preferably at evaporation 30～60nm.
Below, utilize embodiment that its result is described.
(embodiment)
(Floating Zone: the floating region) grow by method with FZ for gallium oxide single crystal (do not have and add).As atmosphere gas, under oxygen concentration 10% (flow-rate ratio), speed of growth 7.5mm/hr, 1 atmospheric condition, grow.Cut out its (100) face, mirror ultrafinish is carried out on the surface, be processed into the wafer-like of the about 0.4mm of thickness with cmp.
As the pre-treatment of substrate, after organic cleaning, carry out 15 minutes processing and use H with HF5%
2SO
4: H
2O
2: H
2O=4: mixed liquor carried out 5 minutes processing in 1: 1.
To this sample, in the oxygen atmosphere 1100 ℃ of heat treatments of carrying out 3 hours and 6 hours.
Then, as the pre-treatment of electrode evaporation material, carry out plasma irradiating.As a comparative example, do nothing processing when only carrying out grinding 10 μ m with diamond chip.By carrying out plasma irradiating at sample from the plasma irradiating that residual gas (oxygen nitrogen) produces.
After these were handled, behind the Ti of evaporation 50nm, the Au of evaporation 100nm was made into electrode.At this moment electrode size is that diameter is the circle about 1mm.And several to (between AuTi) between these terminals measure current-voltage characteristic.
Fig. 2 represents the interelectrode current-voltage characteristic of AuTi.Heat treatment time is 3 hours, after this heat treatment,, (a) be result when not handling as the evaporation pre-treatment of electrode material, (b) being result when grinding 10 μ m with diamond chip, (c) is the result when having carried out 30 minutes the processing of oxygen nitrogen plasma irradiation.
Fig. 3 represents that heat treatment time is the equifinality under 6 hours the situation.Untreated situation (a) electric current flows with the nA magnitude, can not be used as electrode.When grinding 10 μ m, streaming current still only flows through the electric current (b) of maximum μ A magnitudes substantially often.When carrying out plasma irradiating, on all electrodes, flow through the electric current (c) of mA magnitude.
As can be known: because the IV characteristic is not a straight line, so the ohm fully of can not saying so, still the easiest streaming current under the situation of having carried out plasma irradiating can confirm effect.
Below, according to carrying out the situation that ohm connects, the ultraviolet ray photodetector that uses gallium oxide is described to above-mentioned gallium oxide single crystal.
High-quality piece (bulk: gallium oxide (Ga body)
2O
3) monocrystalline has: band gap is about 4.8eV (about 260nm), can detect the following ultraviolet characteristic of wavelength 280nm selectively.Further because have conductivity, so can be directly at Ga
2O
3Monocrystalline obtains electrode.Further because be oxide, the oxidation so task need not be worried as other above-mentioned semiconductor and deterioration have superior characteristic in durability, aspect stable.Present embodiment is at high-quality piece gallium oxide (Ga
2O
3) present inventor that achieves success of the growing method aspect of monocrystalline etc., conscientiously discussed UV sensor (ultraviolet ray photodetector) and the manufacture method thereof of utilizing this specific character and finished.
About becoming the Ga of material
2O
3Monocrystalline can be manufactured on the superior monocrystalline in crystal quality aspect with the method that present inventors have invented.This method is, with the Ga of purity 4N
2O
3Powder is enclosed in the rubber tube as raw material, is shaped with rubber pattern press (rubber press), and be fuel rod with the sintered body that in electric furnace, obtained in 10 hours, with FZ (FloatingZone) method growing single-crystal at 1500 ℃ of sintering.As the crystal growth condition, the speed of growth is 5～10mm/h, and atmosphere is dry air, and pressure is 1 atmospheric pressure, carries out with this understanding.
Monocrystalline to such making, with the strongest parallel face of (100) face of steel wire sawing and riving property, (CMP:Chemical Mechanical Polishing) carries out mirror ultrafinish to this (100) face with chemical mechanical milling method, is processed into the wafer-like of thickness 0.4～0.5mm.
The Ga of Zhi Zuoing like this
2O
3Monocrystalline, resistivity are 1～5 * 10
-1Ω cm, carrier density is 10
17～10
18Cm
-3, have conductivity.It is used as the substrate manufacture UV sensor.
In execution mode 2, the ultraviolet ray photodetector (transducer) of vertical structure is described.Fig. 4 is the side view of expression sensor construction.Transducer shown in Figure 4 (ultraviolet ray photodetector) is provided with electrode 7,5 at the surface and the back side of gallium oxide single crystal substrate 10, makes vertical Schottky diode.Make Schottky electrode on the surface, make Ohmic electrode overleaf.At this moment, under electrode 7 bottoms on surface, form depletion layer 3a, under depletion layer 3a, form conductive layer 3b.
For light being transformed into electron hole pair and detecting, need to make the resistive formation that sandwiches between the electrode.This be because, if conductive formation then electric current flow through simply, then can not isolate photoelectric current.
In order to make this resistive formation, utilize high-resistance film, or, wherein utilize the method for depletion layer, because have amplification and high sensitivity, so more satisfactory to making resistive formation based on the method for the depletion layer of Schottky contacts, pn knot.Further, about the making of depletion layer, be Ga
2O
3The time, because be merely able to obtain the n type, be based on the depletion layer of Schottky contacts so preferably be not based on the pn knot.The result is that the structure of detector becomes Metal-Semiconductor-Metal (MSM: type metal-semiconductor-metal).
In the MSM type, has horizontal type and vertical.When being horizontal type, need utilize formation comb poles such as photoetching.Because this comb poles is difficult to realize large tracts of landization, be merely able under electrode, form depletion layer, so Ga
2O
3Utilization ratio reduce.
Relative therewith, with regard to vertical, as shown in Figure 4, sensor part is following simple structure: be formed with on the surface light receiving surface 7a thin translucent (or transparent) electrode (Schottky electrode: first electrode) 7, only form electrode (Ohmic electrode: second electrode) 5 overleaf.Different with horizontal type, because whole of the depletion layer 3a that can expand in the transparency electrode bottom receives light, so Ga
2O
3The utilization ratio height of monocrystalline, so simple in structure because do not need to make comb poles again, it is easy that technology also becomes, and has aforesaid advantage.
Below, explain use Ga according to each technology
2O
3The manufacture method of the device of the vertical structure of monocrystalline.Fig. 5 represents whole operations of element manufacturing.
(S1: the annealing of monocrystalline)
At first, clean substrate, heat-treat with fluoric acid, sulfuric acid, acetone, ethanol, pure water.Because the Ga after crystal growth
2O
3Residual defectiveness etc. in the monocrystalline is so heat-treat in order to make its recovery.In oxygen atmosphere 1100 ℃, carry out 3～24 hours heat treatment.If use the time than 3 hours weak points, then the recovery of crystallographic is insufficient, even if the change expense than the processing time of 24 little durations, also because roughly saturated, characteristic no longer changes.Using oxygen is in order to replenish growth Ga
2O
3The oxygen that takes place during monocrystalline is damaged.
(S2: form diaphragm on the surface)
Because plasma irradiating is carried out at the back side, so for fear of the damage on surface and at pre-irradiation coating diaphragm 4.In diaphragm 4, use for example to be used for fixing the fixing cured etc. of analytical sample.Because should fixing cured grade near 100 ℃, melt,, be pressed in Ga so it is coated on the sliding glass
2O
3The surface of substrate makes its cooling back just can prevent that the surface is subjected to ion exposure
(S3: plasma irradiating is carried out at the back side)
In order to obtain ohmic contact overleaf, further, carry out plasma irradiating in order to improve conductivity and to realize low resistanceization.This is in order to generate defective forcibly, to improve conductivity by producing carrier electrons.Utilize the low pressure glow discharge of using residual gas, to sample back side illuminaton plasma.
Ionic current is hundreds of μ A, and the electric current of whole device is 5～10mA.Irradiation time is 20～40min, is preferably 30min.This be because when than 20min in short-term effect lack, even if carry out the long also roughly the same cause of radiation response of time ratio 40min.
(S4: the diaphragm of removing the surface)
After the back side carried out plasma irradiating, remove diaphragm 4.It is cured to add heat fixation once more, takes Ga off
2O
3Substrate is removed fixing curedly, cleans substrate with acetone.
(S5: form Ohmic electrode overleaf)
(5a, 6a) afterwards, (5b 6b), forms the Ohmic electrode 5,6 of Au/Ti to the Au of evaporation 80～150nm, preferred 80～100nm to the Ti of evaporation 30～70nm, preferred 30～50nm.Making electrode size is 1～5mm φ, is preferably 3～4mm φ.And the big more then contact resistance of sample is more little.
(S6: form Schottky electrode on the surface)
As Schottky electrode material 7,, be Au, Pt etc. so use the big metal of work function because be the n N-type semiconductor N.Behind the Ni (7a) of evaporation 2～5nm, preferred 2nm, the Au of evaporation 6～10nm or Pt (7b), the electrode of making Au/Ni or Pt/Ti translucent (or transparent).Wherein,, the Au, the Pt that do not insert the Ni layer can be used, further except Au, Pt, also Al, Co, Ge, Sn, In, W, Mo, Cr, Cu etc. can be used about metal.
Why evaporation Ni is because the close property of Au or Pt monomer and substrate is bad, improves close property so insert the Ni layer that approaches.It becomes light receiving surface, and electrode size at this moment is 1～5mm φ, preferred 3～4mm φ.The big more then light receiving surface of electrode size enlarges more.
(S7: the formation of pad (pad) electrode)
In this electrode 7, make the pad electrode 8 that distribution is used.The size of pad electrode 8 is 0.05～1.5mm φ, the Ni (8a) of the preferred 4～6nm of evaporation 3～10nm in translucent light receiving surface (electrode 7), 80～150nm preferably～Au or the Pt (8b) of 100nm.In addition, at this moment make the Ohmic electrode 9 (9a:Ni, 9b:Au or Pt) that the bias voltage corresponding with Ohmic electrode 6 used simultaneously.
About the device of making of above such operation, in order to estimate device property, irradiates light is investigated performances such as spectrum analysis sensory characteristic practically.Below, with embodiment its details is described.
(embodiment)
Will gallium oxide powder (purity 4N) enclose in the rubber tube and make its shaping with the hydrostatic press, in atmosphere 1500 ℃ of sintering 10 hours.This sintered body as fuel rod, is carried out crystal growth with light FZ device.Make that the speed of growth is 7.5mm/h, use oxygen 80%-nitrogen 20% (flow-rate ratio) as atmosphere gas.
Cut out (100) face of the monocrystalline that obtains, with CMP its attrition process is arrived thickness 0.4mm, the surface becomes the minute surface of mean roughness～0.2nm, as the substrate of wafer-like.Size of substrate is about 7mm * 8mm.
To this Ga
2O
3Monocrystalline carries out Hall (Hall) to be measured, and the result shows following conductivity: resistivity is 1.2 * 10
-1Ω cm, carrier density is 1.3 * 10
18Cm
-3, mobility is 39cm
2/ Vs.After cleaning this substrate with fluoric acid, sulfuric acid, acetone, ethanol, pure water, in oxygen atmosphere 1100 ℃ of heat treatments of carrying out 6 hours.
Below, according to operation shown in Figure 5, carry out the making of electrode.
At this moment the configuration of electrode as Fig. 6 (a) (b) shown in, with respect to the Ga of 7mm * 8mm
2O
3Size of substrate, electrode size are 4mm φ.The Ohmic electrode at the back side behind the Ti of evaporation 50nm, the Au of evaporation 100nm and forming.In addition, Fig. 6 (a) is the figure that sees the transducer shown in Fig. 4 from the top, and Fig. 6 (b) is the figure that sees the transducer shown in Fig. 1 from the below.
On the other hand, the Schottky electrode on surface, behind the Ni of evaporation 2nm, the Au of evaporation 8nm and forming.The pad electrode that distribution is used is 1mm φ, at evaporation behind the Ni of 5nm, the Au of evaporation 100nm.At this moment, light receiver becomes from the semitransparent electrode of 4mm φ and partly removes part behind the pad electrode of 1mm φ.The photo of Fig. 6 (c) is represented the photodetector of the reality after electrode is made.
The above device of making is like that carried out rayed, estimate current-voltage characteristic, spectrum analysis sensory characteristic.At this moment light source uses deuterium lamp (the system 150WL1314 of Japanese Hamamatsu Photonics K. K (creek pine ホ ト ニ Network ス), water-cooled).The light of irradiation every 10nm beam split from 200nm to 350nm.In addition, Figure 11 is the skeleton diagram of work of the photodetector of the vertical structure of expression in the present embodiment.
(current-voltage characteristic)
During the rayed of Fig. 7 (a) expression upper electrode and lower electrode and current/voltage (IV) characteristic when not shining, i.e. the IV characteristic of photodetector itself.+ be the pad electrode ,-be big Au/Ti electrode (with the opposed electrode of transparency electrode).Can confirm upper electrode from its result is Schottky contacts.
Obtain Fig. 7 (b) with logarithmic table diagrammatic sketch 7 (a).At first, note dark current because+5V and-electric current of 5V is respectively 4.50 * 10
-3A, 1.06 * 10
-9A is so commutating ratio is 10
6Secondly, when irradiates light, there be difference about 3 orders of magnitude in photoelectric current along flowing in the other direction.
(spectrum analysis sensory characteristic)
When to the photodetector device of Fig. 7 (b) irradiation light time after every 10nm beam split from 200nm to 350nm, the power that is radiated at each wavelength on the light receiving surface as shown in Figure 8.Centre wavelength is near 240～250nm as can be known.
Spectrum analysis sensory characteristic during the 10V reverse biased as shown in Figure 9.Become the sun blind (Solar-blind) that has sensitivity at wavelength during less than 280nm as can be known.When with it during divided by irradiation power, it is such to become Figure 10.Remolding sensitivity is about 3 orders of magnitude.
In Figure 10, charged to external quantum efficiency η, but because surpass 100%, so also can change multiplication factor (multiplication factor) and definition.Wherein, make respectively that I, P, λ are photoelectric current, incident power, wavelength, can calculate η by enough following formula.
η＝(I/P)*(1240/λ)
Execution mode 3
In execution mode 2, the transducer of vertical structure has been described, but the present invention also can be applied to the transducer of horizontal type structure, this is self-evident.
Figure 12 is the job description figure of the transducer of the horizontal type structure of explanation.In Figure 12, this transducer is provided with low carrier density layer or insulating barrier 10a on the surface of gallium oxide single crystal substrate 10, be provided with at this low carrier density layer or surface of insulating layer: first electrode 11 with light receiving surface 11a; And and the ultraviolet ray that receives by the light receiving surface 11a of first electrode 11 correspondingly between self and first electrode through Ga
2O
3Second electrode 12 of flow of substrates overcurrent.
In the present embodiment, in the heat treatment of in S1, representing, carry out long heat treatment, up to forming low carrier density layer or insulating barrier than the dark position of light absorption distance.And the comb-type electrode that low carrier density layer after thermal oxidation or surface of insulating layer formation have Au/Ni structure or Pt/Ni structure forms the Ohmic electrode as second electrode 12 in its vicinity as first electrode (corresponding with Schottky electrode) 11.About the formation method of each electrode, corresponding with the method that has illustrated in the execution mode 1.
Like this, form light receiving surface, produce photoelectric current in low carrier density layer below this electrode or the insulating barrier, detect ultraviolet ray, form above-mentioned structure by the electric current that detects between first electrode 11 and second electrode 12 at comb-type electrode.
As described above, vertical structure has does not need large-area comb-type electrode, Ga
2O
3The simple advantage of utilization ratio height and manufacturing process, but think that expeditiously bias voltage is being applied to formed depletion layer this respect, the transducer of horizontal type structure is better.In addition, because carry out long heat treatment, so can will regard insulator near the electrode substantially as, form high potential barrier metal electrode (corresponding) and contacting of insulator and become easy with Schottky electrode, make the little transducer of dark current easily, obtain high sensitivity easily, that is, can obtain aforesaid effect.
Utilizability on the industry
According to the present invention, because do not need film growth, use the gallium oxide (Ga of electric conductivity2O
3) monocrystal substrate, so the durability aspect is superior, can obtain to reduce the effect of the cost that spends in the film growth aspect.
Claims (13)
1. photodetector is used in a ultraviolet ray, it is characterized in that, comprising:
The gallium oxide single crystal substrate;
First electrode, the surface that it is formed at described gallium oxide single crystal substrate has light receiving surface, and constitutes Schottky contacts with described gallium oxide single crystal substrate; With
Second electrode, it is formed at the back side of described gallium oxide single crystal substrate, constitute ohmic contact with described gallium oxide single crystal substrate, and and the ultraviolet ray that receives by described light receiving surface correspondingly between this second electrode and described first electrode through described gallium oxide single crystal flow of substrates overcurrent.
2. photodetector is used in ultraviolet ray according to claim 1, it is characterized in that:
Described first electrode is made of Au or Pt,
Described second electrode is made of Au or Al.
3. photodetector is used in ultraviolet ray according to claim 1, it is characterized in that:
Described first electrode has Au/Ni or the Pt/Ni structure of inserting the Ni layer and form between Au or Pt and described gallium oxide single crystal substrate,
Described second electrode has Au/Ti or the Al/Ti structure that formation Ti layer forms as basalis between Au or Al and described gallium oxide single crystal substrate.
4. use photodetector according to each described ultraviolet ray in the claim 1～3, it is characterized in that:
It is 1～5 * 10 that described gallium oxide single crystal substrate has resistivity
-1Ω cm, carrier density are 10
17～10
18Cm
-3Conductivity, use (100) face of this gallium oxide single crystal substrate.
5. photodetector is used in a ultraviolet ray, it is characterized in that, comprising:
The gallium oxide single crystal substrate, it is formed with low carrier density layer on the surface;
First electrode, it is arranged at the described low carrier density laminar surface of described gallium oxide single crystal substrate, and has light receiving surface; With
Second electrode, it is arranged at the described low carrier density laminar surface of described gallium oxide single crystal substrate, and the ultraviolet ray that receives by described light receiving surface correspondingly between this second electrode and described first electrode through described gallium oxide single crystal flow of substrates overcurrent.
6. a ultraviolet ray is with the manufacture method of photodetector, and this ultraviolet ray is to use the gallium oxide single crystal substrate manufacture with photodetector, and this ultraviolet ray is characterised in that with the manufacture method of photodetector:
Described gallium oxide single crystal substrate is carried out pre-treatment,
Surface at the described gallium oxide single crystal real estate of finishing described pre-treatment forms first electrode that constitutes Schottky contacts with described gallium oxide single crystal substrate, and form second electrode at the back side of described gallium oxide single crystal substrate, this second electrode and described gallium oxide single crystal substrate constitute ohmic contact, and between this second electrode and described first electrode through described gallium oxide single crystal flow of substrates overcurrent.
7. the ultraviolet ray according to claim 6 manufacture method of photodetector is characterized in that:
The back side that described pre-treatment is included in described gallium oxide single crystal substrate is used for the operation that described second electrode carries out the plasma irradiating of ohmic contact,
Described first electrode forms by surperficial evaporation Au or the Pt at described gallium oxide single crystal substrate, and described second electrode is by forming at the back side of the described gallium oxide single crystal substrate that is carried out described plasma irradiating evaporation Au or Pt.
8. the ultraviolet ray according to claim 6 manufacture method of photodetector is characterized in that:
The back side that described pre-treatment is included in described gallium oxide single crystal substrate is used for the operation that described second electrode carries out the plasma irradiating of ohmic contact,
Described first electrode is by the surperficial evaporation Ni at described gallium oxide single crystal substrate, further evaporation Au or Pt and form on this Ni, described second electrode is by at the back side of the described gallium oxide single crystal substrate that is carried out described plasma irradiating evaporation Ti, further evaporation Au or Pt and form on this Ti.
9. a ultraviolet ray is with the manufacture method of photodetector, and this ultraviolet ray is to use the gallium oxide single crystal substrate manufacture with photodetector, and this ultraviolet ray is characterised in that with the manufacture method of photodetector:
Form low carrier density layer or insulating barrier on the surface of described gallium oxide single crystal substrate,
Described low carrier density layer or surface of insulating layer at described gallium oxide single crystal substrate form first electrode and second electrode, this first electrode has light receiving surface, and the ultraviolet ray that receives by described light receiving surface correspondingly between this second electrode and described first electrode through described gallium oxide single crystal flow of substrates overcurrent.
10. the ultraviolet ray according to claim 6 manufacture method of photodetector is characterized in that:
When gallium oxide single crystal formed Ohmic electrode, evaporation Ti after plasma irradiating is carried out on the surface afterwards, formed the electrode that evaporation has Au/Ti structure, Pt/Ti structure or the Al/Ti structure of Au, Pt or Al.
11. the ultraviolet ray according to claim 10 manufacture method of photodetector is characterized in that:
The plasma irradiating plasma that to be irradiation generate from the residual gas that comprises oxygen nitrogen or hydrogen.
12. the ultraviolet ray according to claim 10 manufacture method of photodetector is characterized in that:
The gallium oxide substrate is carried out the gas ions pre-irradiation, in 1100 ℃ oxygen atmosphere, the gallium oxide substrate is being carried out heat treatment more than 3 hours.
13. the ultraviolet ray according to claim 6 manufacture method of photodetector is characterized in that:
Carrying out in the electrode material of ohmic contact with gallium oxide, under situation with described Au/Ti structure, the thickness of electrode material Au/Ti is to be 30～60nm from gallium oxide substrate-side Ti, and Au is 80～150nm, forms these electrode materials by evaporation, sputter or ion plating method.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007301235A JP5103683B2 (en) | 2007-11-21 | 2007-11-21 | Method of manufacturing electrode for gallium oxide substrate and electrode for gallium oxide substrate manufactured thereby |
| JP2007-301235 | 2007-11-21 | ||
| JP2007301234A JP2009130012A (en) | 2007-11-21 | 2007-11-21 | Photodetector for ultraviolet and method for manufacturing the same |
| JP2007-301234 | 2007-11-21 | ||
| PCT/JP2008/070951 WO2009066667A1 (en) | 2007-11-21 | 2008-11-18 | Photodetector for ultraviolet and method for manufacturing the photodetector |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101868862A true CN101868862A (en) | 2010-10-20 |
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ID=40667489
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200880117234A Pending CN101868862A (en) | 2007-11-21 | 2008-11-18 | Photodetector for ultraviolet and method for manufacturing the photodetector |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR20100087017A (en) |
| CN (1) | CN101868862A (en) |
| WO (1) | WO2009066667A1 (en) |
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| CN102496648A (en) * | 2011-11-28 | 2012-06-13 | 南京大学 | Ultraviolet light single-photon detector with built-in negative feedback metal-semiconductor-metal structure |
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| CN107993934A (en) * | 2017-12-08 | 2018-05-04 | 中国科学院微电子研究所 | Strengthen the method for gallium oxide semiconductor device ohmic contact |
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| JPS62115391A (en) * | 1985-11-13 | 1987-05-27 | Nippon Mining Co Ltd | Cdte radiant ray detector |
| JP2000174294A (en) * | 1998-12-08 | 2000-06-23 | Mitsubishi Cable Ind Ltd | Photoconductive element |
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| JP2007137727A (en) * | 2005-11-18 | 2007-06-07 | Nippon Light Metal Co Ltd | Method for production of gallium oxide single crystal composite, and method of producing nitride semiconductor film using the same |
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2008
- 2008-11-18 KR KR1020107011086A patent/KR20100087017A/en not_active Application Discontinuation
- 2008-11-18 CN CN200880117234A patent/CN101868862A/en active Pending
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Also Published As
| Publication number | Publication date |
|---|---|
| KR20100087017A (en) | 2010-08-02 |
| WO2009066667A1 (en) | 2009-05-28 |
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Open date: 20101020 |