CN105161486B - Tetracarboxylic acid dianhydride organic layer photoelectrical coupler and preparation method thereof - Google Patents
Tetracarboxylic acid dianhydride organic layer photoelectrical coupler and preparation method thereof Download PDFInfo
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Abstract
Tetracarboxylic acid dianhydride organic layer photo-coupler, including the photophore and light-receiving device being assembled in the metal shell of same sealing, photophore are GaAs infrared light-emitting diode chips, and light-receiving device is tetracarboxylic acid dianhydride photodetector electrode chip.Tetracarboxylic acid dianhydride photodetector electrode chip, including the gold electrode layer of lamination, P Si substrate layers, tetracarboxylic acid dianhydride single crystal membrane layer and ito film layer successively, ito film layer surface are equipped with nickel film layer, and nickel film surface is equipped with aluminum membranous layer；Nickel film layer and aluminum membranous layer compositing chip electrode, a diameter of 50 μm of chip electrode.It is made using tetracarboxylic acid dianhydride organic photodetector chip as light-receiving device, using GaAs infrared light-emitting diodes as photophore.Its small, function admirable, broadband response, photoelectric conversion efficiency are up to more than 98%, and the opto-electronic conversion quantum efficiency clutch of the optical coupler combined than silicon photodiode and triode improves 20%, and manufacture cost is the 50% of single crystal silicon device.
Description
Technical field
The invention belongs to microelectronics and photoelectronics novel semi-conductor optoelectronic device technology field, and in particular to a kind of
Tetracarboxylic acid dianhydride organic layer photo-coupler, the invention further relates to the production method of tetracarboxylic acid dianhydride organic layer photo-coupler.
Background technology
Photo-coupler（Optical coupler, english abbreviation OC）, it is called photoelectricity optical coupler.It is that light passes for medium
Light-electro-optical conversioning device of power transmission signal.The device is assembled in the housing of same sealing by light emitting source and light-receiving device two parts
It is interior, isolated to each other with transparent insulating substrate.The pin of light emitting source is input terminal, and the pin of light-receiving device is output terminal.Common hair
Light source is light emitting diode, and light-receiving device is the photodetectors such as photodiode, phototriode.Photo-coupler input terminal powers up
The illumination that signal sends light emitting source is mapped to light-receiving device generation photoelectric current and is drawn by light-receiving device output terminal, turns so as to fulfill light-electricity
Change.Different luminescent devices and the combination of various optical receiving sets may make up various photo-couplers various in style, photo-coupler is
As a kind of unique semiconductor devices.With the digitlization of signal processing in recent years, the systematization of high speed, instrument/instrument
And the development of networking, photodiode add the photo-coupler of amplifier class in Light Electronic Control System, photoelectric communication field and each
It is widely used in kind circuit.Market demand constantly increases.
With the development of science and technology and the continuous of application range extends, and proposes higher to photo-coupler performance and wants
Ask.Existing photo-coupler is entirely the photodiode and phototriode made using monocrystalline silicon.In fact, photo-coupler
It is a kind of electric current transferring device by photoelectricity flow control, linear working range is relatively narrow, and varies with temperature and change；By monocrystalline silicon
Its reverse saturation current of the semiconductor devices of making Iceo（That is dark current）It is acted upon by temperature changes fairly obvious, makes circuit work
The stability and reliability of work are affected；And the photoelectric conversion efficiency of silicon photodiode and phototriode is not high, only
Have 78%；And production cost is higher.
Developing rapidly for organic optoelectronic and organic chemistry, is greatly promoted the wound of novel organic semi-conductor device
Newly.We take the lead in having carried out organic semiconductor material under the subsidy of state natural sciences fund and Gansu Province's Natural Science Fund In The Light
Expect tetracarboxylic acid dianhydride（3,4,9,10 perylenetetracarboxylicdianhydride abbreviations PTCDA）Synthesis
And its further investigation of physical property is drawn a conclusion：Tetracarboxylic acid dianhydride can be formed in order on various inorganic material substrates
Layer, and there is monoclinic structure；Energy between its valence band and the first tight-binding conduction band is 2.2ev；Each structure cell contains
There are two molecules；Molecular weight is 392, its density is 1.69g/cm3, sublimation temperature is 450 DEG C；When wavelength X is in 0.5~1.0 μ
When changing in the range of m, its absorption coefficient of light α0Excursion is 102cm-1~104cm-1.Utilize this dyeing of organic material, energy
Enough methods by vacuum evaporation, form the molecule layer film of high quality on the surface of inorganic semiconductor p-Si and have Schottky
Barrier properties.
Electrode chip has been made using tetracarboxylic acid dianhydride in inventor, which obtains utility model patent, its is entitled
《PTCDA/P-Si heterojunction photoelectric detector low-resistance ohmic electrode chips》, Patent No. ZL201120070565.9.The patent
The production method for disclosing a diameter of 150 μm of Ohmic electrodes of photodetector electrode chip.On this basis, in order to make this width
The performance of the photodetector of frequency band high-quantum efficiency is improved and widens its application, we further optimize the device
Structural parameters, make in 6 Rotating fields per layer film thickness by theory analysis and calculating make its more rationally and it is feasible；And P-
Si monocrystalline back electrodes Al is changed to the Au with ductility and wettability, reduce further the contact resistance of back electrode, carries
The high photoelectric properties of device；In addition, the diameter of chip electrode is changed to 50 μm, while the surrounding of each chip by 150 μm
Edge makes width by lithography and is changed to 30 μm by original 50 μm, adds the light-receiving area of ito film, further increases the device
The efficiency of the opto-electronic conversion of part.Make the photodetection of this broadband high-quantum efficiency by said structure improvement and process practice
The performance of device has obtained increasing substantially raising.The test report that in August, 2014 is provided through China Testing Technology Institute shows,
It has response to light of the wavelength in 450nm~1100nm（I.e. it can will be changed into electric energy in the luminous energy of the wavelength band）, it is
A kind of good broadband light electronic component of responsiveness.The test curve of wavelength and responsiveness from incident light immediately arrives at, it
There is the peak value of maximum to the light of 930nm, it is emphasized that it to the light that wavelength is 930nm, its absorption coefficient of light is 1, i.e. table
Show that it can all absorb incident light, the quantum efficiency of its opto-electronic conversion is up to 100%.This wavelength is just red with GaAs
The wavelength that UV light-emitting diode sends light is identical.Photoelectric conversion efficiency can be produced by, which being combined using both, is bordering on 100%
Tetracarboxylic acid dianhydride photo-coupler.
The content of the invention
The first object of the present invention is to provide a kind of tetracarboxylic acid dianhydride small, cost is low, photoelectric conversion efficiency is high
Organic layer photo-coupler；The second object of the present invention is to provide the manufacture method of tetracarboxylic acid dianhydride organic layer photo-coupler.
In order to realize above-mentioned first purpose, the technical solution that the present invention takes is as follows：A kind of tetracarboxylic acid dianhydride organic layer
Photo-coupler, including the photophore and light-receiving device being assembled in the metal shell of same sealing, it is characterised in that：Photophore is
GaAs infrared light-emitting diode chips, light-receiving device are tetracarboxylic acid dianhydride photodetector electrode chip.
Tetracarboxylic acid dianhydride photodetector electrode chip, including the gold electrode layer of lamination, P-Si substrate layers, four successively
Formic acid dianhydride single crystal membrane layer and ito film layer, ito film layer surface are equipped with nickel film layer, and nickel film surface is equipped with aluminum membranous layer；Nickel film layer
With aluminum membranous layer compositing chip electrode, a diameter of 50 μm of chip electrode.
The length of side of the gold electrode layer of lamination, P-Si substrate layers and tetracarboxylic acid dianhydride single crystal membrane layer is 3000 μm, ito film
The length of side of layer is 2940 μm.
Photo-coupler provided by the invention using tetracarboxylic acid dianhydride organic photodetector chip as light-receiving device, it is red with GaAs
UV light-emitting diode is made for photophore.Its small, function admirable, broadband response, photoelectric conversion efficiency up to 98% with
On, the opto-electronic conversion quantum efficiency clutch of the optical coupler combined than silicon photodiode and triode improves 28%, manufactures cost
It is the 50% of single crystal silicon device.Photo-coupler provided by the invention is with good stability and reliability, applied to computer and
In various electronic circuits.
In order to realize above-mentioned second purpose, the technical solution that the present invention takes is as follows：A kind of tetracarboxylic acid dianhydride organic layer
The manufacture method of photo-coupler, it is characterised in that carry out as steps described below：Au-Si ohmic contact layers are made, in Si pieces front
Deposit tetracarboxylic acid dianhydride film, deposition ito film, high-purity N i films and high-purity Al films, etching Al-Ni electrode lead holes with it is every
The edge of a chip etches the step that width is 30 μm, thermal compression welding tetracarboxylic acid dianhydride chip and GaAs infraluminescences
Diode chip for backlight unit；Specific method is as follows：
A, Au-Si ohmic contact layers are made
By 350 μm of thickness, 2 Ω cm of resistivity, the indices of crystallographic plane 100, it is polished after p-type single crystalline Si piece cleaned
Processing：Toluene, carbon tetrachloride, acetone, each ultrasonication 5mim of absolute ethyl alcohol are used successively, then using deionized water rinsing；
Through H2SO4Boil after 3min is cooled to room temperature again with a large amount of deionized water rinsings；Through volume ratio H2O：HF is 9：1 corrosive liquid
Microprocessor 15 seconds, after repeatedly being rinsed with deionized water again, is dried under infrared lamp；The Si pieces are placed on high vacuum with fixture
In heating coating equipment, treat vacuum up to 5 × 10-3During Pa, in the Au of the back side of Si pieces evaporation 200nm in high vacuum vapor deposition room
After film, and lead to H in alloying furnace2Gas, constant temperature 6 minutes at a temperature of 385 DEG C, form Au-Si ohmic contact layers；
B, in Si pieces front deposition tetracarboxylic acid dianhydride film
Under high vacuum state, tetracarboxylic acid dianhydride is deposited into the thin of 100nm for 450 DEG C in its sublimation point to Si pieces front
Film, uses model Rigaku-D/max-2400 powder x-ray diffractions；Using Cu target K α radiations, its X-ray wavelength is
0.154056nm, pipe pressure is 40kv, and Guan Liuwei 150mA, the angle of diffraction is 2 θ=50~1000, 2 θ sweep speeds are 50/ min, scanning
2 θ of step-length △ are 0.020, it is 10 seconds often to walk the sampling time；Under these conditions, four in single crystalline Si piece surface deposition are measured
Formic acid dianhydride only has α-PTCDA mutually to exist, i.e., tetracarboxylic acid dianhydride forms monoclinic structure in the clean surface of single crystalline Si piece；
The interface of monoclinic structure and Si pieces forms homotype hetero-junctions；
C, ito film, high-purity N i films and high-purity Al films are deposited
It is sequentially depositing ito film, high-purity N i films, high-purity Al respectively on the above-mentioned surface for having deposited tetracarboxylic acid dianhydride film
Film.The effect of Ni films is to prevent Al from reacting with ITO, prevents Al and O to react to form Al2O3, improve photoelectricity spy
Survey the stability and reliability of device；Wherein the thickness of ITO nesa coating is 150nm；The thickness of Ni films is 50nm；Al films
Thickness be 250nm；The substrate is in 150 DEG C of logical H2The substrate of 3 minutes obtained six layer structures of microalloying in the alloying furnace of gas；
D, the edge for etching Al-Ni electrode lead holes and each chip etches the step that width is 30 μm
The AlNi electrode lead holes of 50 μm of φ are etched using microelectronics planar technology photolithography method, and in each chip
The edge of ITO nesa coating make the step that width is 30 μm, bottom is tetracarboxylic acid dianhydride surface by lithography；Photoetching work
In skill：Using positive photoresist, corresponding supporting have positive photoresist dilution, positive-tone photo glue developing solution and positive photoresist
Go film liquid；
Utilize ultraviolet hard mask contact exposure；Concretely comprise the following steps：
D.1 Substrate treatment is low at a temperature of 80 DEG C in an oven to dry 30 minutes；
D.2 gluing, configuration positive photoresist is applied in Al film surfaces；
D.3 front baking, is baked 30 minutes at a temperature of 150 DEG C in an oven；
D.4 expose, exposed according to common process；
D.5 develop；According to common process positive photoresist developing liquid developing；
D.6 rinse；Rinsed according to common process
D.7 dry afterwards, 100 DEG C, 20 minutes of post bake；
D.8 etched using lithography layout using normal photolithographic process in the edge of each chip I TO nesa coatings
Go out the step that width is 30 μm；
D.9 dedicated potassium permanganate corrosive liquid is used, which can retain the AlNi electrodes with 50 μm of photoresist φ
Lead hole pattern, and the AlNi alloy firms outside AlNi electrode lead holes are corroded to clean, the ito thin film obtained after corrosion
Surface it is straight and even, it is bright, do not produce any stain；
D.10 film liquid is gone to remove the photoresist after photoetching corrosion in contact conductor hole pattern using positive photoresist；
D.2, the preparation method for the configuration positive photoresist that step uses is：Under the red light of darkroom, by 10g positive photoresists
150ml positive photoresist dilutions are dissolved in, is sufficiently stirred with clean glass bar and is allowed to be completely dissolved, and 24 are stood in camera bellows
After hour, using hole after 5 μm of sand core funnel is filtered using attraction method, configuration positive photoresist is obtained, will be configured just
Property photoresist be fitted into dark-coloured ground glass stoppered bottle preserve at normal temperatures it is stand-by；
D.9, the configuration potassium permanganate that step uses corrodes liquid and preparation method thereof：By 3 grams of potassium permanganate and 1 gram of sodium hydroxide
Add in 100ml deionized waters and mix to uniform, obtain configuration potassium permanganate corrosive liquid；
E, thermal compression welding tetracarboxylic acid dianhydride chip and GaAs infrared light-emitting diode chips
By the above-mentioned tetracarboxylic acid dianhydride big circular slice for being carved with electrode lead hole, scribing under the microscope forms 9mm2Core
Piece, 9mm2Chip and GaAs infrared light-emitting diodes chip the metal of circular top end opening is fixed on the method for thermal compression welding
On the stem of shell, and cured with high transparency epoxy encapsulation.
The tetracarboxylic acid dianhydride photodetector that photoelectrical coupler of the present invention is applied is made, its is small, is only 9mm2,
The ratio of saturation photocurrent and dark current is more than 10 at low manufacture cost, broadband response and peak wavelength3, can be various
Reliable and stable use in circuit.
Patent of the present invention is to use microelectronic component planar technology, makes structure every for Al/Ni/ITO/PTCDA/P-Si/Au
The thickness of layer film is more rationally and feasible；And P-Si monocrystalline back electrodes Al be changed to have ductility and can lubricant nature Au, into
One step reduces the contact resistance of back electrode.Wherein the thickness 50nm of Ni films, its effect are to prevent Al and ITO（Indium tin aoxidizes
Thing nesa coating）React, prevent Al and O to react to form Al2O3, improve the photodetector stability and can
By property.In addition, bottom surface and P-Si rear-face contacts is Au films, by microalloy treatment, form the device good low
Ohmic contact layer is hindered, is conducive to the raising of device photoelectric performance.
In the making in lead hole in surface of the present invention, using the plane photoetching process in micro- electricity, make Al-Ni after etched
The diameter of electrode lead hole narrows down to 50 μm.The corrosive liquid containing potassium permanganate is selected in etching, is maintained around fairlead
Burr is not produced, improving the proof voltage of device and can reduce dark current.At the same time also extend nesa coating ITO by
Light area, makes photoelectric conversion efficiency be improved.
The photodetector made by tetracarboxylic acid dianhydride as organic layer, that is, make product tetracarboxylic acid dianhydride of the present invention
Tetracarboxylic acid dianhydride organic photodetector chip used in organic layer photo-coupler, in August, 2014 is through Chinese measuring technology
Photosensitive parameter testing has been done by research institute, and the test certificate main contents that China Testing Technology Institute provides are shown in Table 1 and Fig. 5.
Clearly learnt from table 1 and Fig. 5, the photodetector that PTCDA makes as organic layer, to 450nm~1100nm's
Light has response, and maximum for its responsiveness of the position of 930nm in wavelength, its absorption coefficient of light is 1, represents that it can to incident light
With whole absorptions, the quantum efficiency of its opto-electronic conversion is up to 100%.This wavelength is sent with GaAs infrared light-emitting diodes just
The wavelength of light is identical.Prompting can produce the tetracarboxylic acid dianhydride light that photoelectric conversion efficiency is bordering on 100% using both combinations
Coupler.
On this basis, in March, 2015 tests the photoelectric parameter of the device through state-run 8th July 1st factory in the sky and water comprehensively, surveys
Test result is shown in Table 2.From table 2 it can be seen that by tetracarboxylic acid dianhydride make photodetector bias be 1.5V, 1000lx
Under the white light of (lux), its photoelectric current is in 80 μ A or so, its electrical parameter is than more uniform, its dark current is in 10nA or so.
It is significantly less than the dark current of the photodiode made using single crystalline Si.Meanwhile as seen from Table 2, it is inclined in no light 1.5V
Under pressure effect, its dark current is measured in 10nm or so, the ratio between its photoelectric current and dark current are 103（I.e. photoelectric current is dark current
1000 times）, since dark current is very faint, the noise current that it is produced in circuit is also very small.It is it follows that this new
Tetracarboxylic acid dianhydride photodetector using in circuit（Photo-coupler including making）, there is extraordinary working status；
In addition, in low temperature（-55℃）And high temperature（125℃）Under conditions of recycling storage 8 it is small when, surveying its electrical parameter, to find no deterioration existing
As illustrating the electrical parameter of the organic photodetector from the influence of the change of its environment temperature, having very good reliable
Property and stability.
Tetracarboxylic acid dianhydride organic layer photo-coupler provided by the invention has produced product, and in December, 2014
Commission Beijing Rui Pubei Photoelectron Corp. has carried out it test of photoelectric parameter, test result and has been shown in Table 3.In July, 2015,
Physics technical college of Lanzhou University has also carried out electrical parameter test to tetracarboxylic acid dianhydride organic layer photo-coupler, test
It the results are shown in Table 4.
Found out by the test result of table 3, the electrical parameter of this new photo-coupler complies fully with the said firm's similar product
Quality index.
As can be seen from Table 4, the input/output transmission characteristic of tetracarboxylic acid dianhydride organic layer photo-coupler of the present invention, every
Parameter and photoelectric properties from characteristic are fully meet by the photosensitive diode chip that Si makes and GaAs infrared light-emitting diodes
The technical indicator of the photo-coupler of chip portfolio.Further, since dark current be greatly lowered and the raising of breakdown reverse voltage,
So as to enhance stability and reliability that it is used in circuit；The quantum efficiency of its photoelectric conversion has reached more than 98%, than
The opto-electronic conversion quantum efficiency of silicon photosensitive diode chip and the optical coupler of triode chip combination improves 20%, and manufacture cost is
The 50% of single crystal silicon device.It can substitute the photo-coupler of the photosensitive two pole pieces piece pipe compositions of Si in similar product completely；Together
When, the input characteristics of the photo-coupler is determined by GaAs light-emitting diode chip for backlight unit it can be seen from the test data in table 4；So
And output characteristics is determined by the tetracarboxylic acid dianhydride optocoupler chip as light-receiving device completely, its dark current is very small, in nA
The order of magnitude；Its breakdown reverse voltage is in 90V or so；It has signal good transmission characteristic, and the electricity that isolation characteristic is measured
Appearance is very small, in 2-3PF（Micromicrofarad）；Its insulation resistance is up to 1010Ω, realizes the completely isolated of electrical property.It is defeated by its
Enter the photoelectric parameter testing one by one of characteristic, output characteristics, transmission characteristic and isolation characteristic the result shows that, light provided by the invention
Coupler, which has, to be suppressed to disturb and eliminate the characteristic of noise well.These characterisitic parameters and Xiamen Hua Lian photoelectric technology responsibility
The product of Co., Ltd and Beijing Rui Pu Photoelectron Corp. is compared, and has reached its parameter and standard, and individual parameters are also excellent
In the numerical value of the product of above-mentioned company, the completely isolated with very good reliability and stability of electrical property is realized, it is complete
The reliable and stable use in various circuits entirely；It has wide purposes and market prospects in computer and electronic circuit.
Brief description of the drawings
Fig. 1 is the structure diagram of photo-coupler of the present invention；
Fig. 2 is the diagrammatic cross-section of tetracarboxylic acid dianhydride photoelectric detector chip；
Fig. 3 is the X-ray diffraction of the tetracarboxylic acid dianhydride of deposition on single crystalline Si piece surface when making photo-coupler of the present invention
Figure；The abscissa of the figure represents that angle of diffraction is 2 θ, and ordinate is the relative intensity of diffraction maximum；
Fig. 4 is to utilize microelectronics planar technology photolithography method, in a diameter of 50 μm of Al- of the surface etch of ito thin film
Ni electrode lead holes, make photolithography plate figure of the width for 30 μm of step by lithography in the edge of each chip；
Fig. 5 is the spectral response curve figure of tetracarboxylic acid dianhydride organic photodetector chip, and abscissa is incident light
Wavelength（Wavelength interval 10nm）, ordinate is peak response degree.
In figure：1-GaAs infrared light-emitting diode chips, 2-tetracarboxylic acid dianhydride photoelectric detector chip, 3-metal
Housing, 4-gold electrode layer, 5-P-Si substrate layers, 6-tetracarboxylic acid dianhydride single crystal membrane layer, 7-ito film layer, 8-nickel film layer,
9-aluminum membranous layer, H1-gold electrode layer thickness, H2-P-Si substrate layer thickness, H3-tetracarboxylic acid dianhydride single crystal membrane layer thickness,
H4-ito film layer thickness, H5-nickel thicknesses of layers, H6-aluminium film layer thickness, a-mask graph square length of side, b-etching platform
Rank width, the spacing of c-Al-Ni contact conductors bore edges and ito film left end, d-Al-Ni contact conductor bore dias, e-Al-
Ni contact conductors bore edges and the spacing of ito film upper end.
Embodiment
Product embodiments, as shown in Figure 1：A kind of tetracarboxylic acid dianhydride organic layer photo-coupler, including be assembled in same close
Photophore and light-receiving device in the metal shell 3 of envelope, photophore are GaAs infrared light-emitting diodes chip 1, light-receiving device four
Formic acid dianhydride photodetector electrode chip 2.Metal shell 3 is the metal shell of top end opening, and high transparency epoxy resin injects
Metal shell, by two chips in electrically completely insulated encapsulation.
Referring to Fig. 2：Tetracarboxylic acid dianhydride photodetector electrode chip, including the gold electrode layer 4 of lamination, P-Si linings successively
Bottom 5, tetracarboxylic acid dianhydride single crystal membrane layer 6 and ito film layer 7,7 surface of ito film layer are equipped with nickel film layer 8, and 8 surface of nickel film layer is set
There is aluminum membranous layer 9；Nickel film layer 8 and 9 compositing chip electrode of aluminum membranous layer, a diameter of 50 μm of chip electrode.
The length of side of the gold electrode layer 4 of lamination, P-Si substrate layers 5 and tetracarboxylic acid dianhydride single crystal membrane layer 6 is 3000 μm, ITO
The length of side of film layer 7 is 2940 μm.
Gold electrode layer thickness H 1 is 200nm, and P-Si substrate layer thickness H2 is 350 μm, tetracarboxylic acid dianhydride single crystal film thickness
Degree H3 is 100 nm, and I TO thicknesses of layers H4 is 150 nm, and nickel thicknesses of layers H5 is 50 nm, and aluminium film layer thickness H6 is 250 nm.
Thickness is 350 μm of P-Si（100）The Au layers of 200nm have been deposited below single crystalline substrate, have formd Ohmic contact
Layer；In P-Si（100）The tetracarboxylic acid dianhydride of 100nm has been deposited above single crystalline substrate（PTCDA）Single crystal membrane layer, both boundaries
Face forms homotype hetero-junctions, has Characteristics of Schottky Barrier, there are electric field and potential in potential barrier.In deposited tetramethyl
The surface of acid dianhydride is using the ITO nesa coating of the method deposit thickness 150nm of sputtering, the sputtering sedimentation 50nm on its surface
High-purity N i（Purity is 99.99%）Film, and then high-purity Al of sputtering 250nm（Purity is 99.99%）Film, and in temperature
For 150 DEG C, and microalloying 3 minutes in the alloying furnace of hydrogen are passed through, six layers of knots of Al/Ni/ITO/PTCDA/P-Si/Au are made
The substrate of structure.The effect of Ni films is to prevent Al from reacting with ITO, prevents Al and O to react to form Al2O3, improve the light
The stability and reliability of electric explorer.
Embodiment of the method, tetracarboxylic acid dianhydride light is made using the planar technology that semiconductor Si devices are manufactured in microelectronics
Electric explorer electrode chip, then by tetracarboxylic acid dianhydride photodetector electrode chip and GaAs infrared light-emitting diode cores
Piece, with the stem for the metal shell that circular top end opening is fixed on high transparency epoxy encapsulation；Implement specific steps
It is as follows：
1st, by 350 μm of thickness, 2 Ω cm of resistivity, the indices of crystallographic plane 100, it is polished after p-type single crystalline Si piece carry out it is clear
Clean processing：Successively with after toluene, carbon tetrachloride, acetone, each ultrasonication 5mim of absolute ethyl alcohol, deionized water rinsing is used；
Through H2SO4Boil after 3min is cooled to room temperature again with a large amount of deionized water rinsings；Through H2O：HF（9：1）Corrosive liquid microprocessor 15
Second, to remove the oxide-film on Si pieces surface, and dried after repeatedly being rinsed with deionized water again under infrared lamp.Will with fixture
The Si pieces are placed in high vacuum heating coating equipment, treat vacuum up to 5 × 10-3 PaWhen, in Si pieces in high vacuum vapor deposition room
The back side evaporation 200nm Au films after, and in alloying furnace lead to H2Gas, constant temperature 6 minutes at a temperature of 385 DEG C, form
Au-Si ohmic contact layers（Such as the interface of the P-Si substrate layers 5 in Fig. 2 and Au films 4）.
2nd, under high vacuum state, the film by tetracarboxylic acid dianhydride in its sublimation point to Si pieces front deposition 100nm, it
Monoclinic structure is formed in the clean surface of single crystalline Si piece, uses model Rigaku-D/max-2400 powder x-ray diffractions
Instrument；Using Cu target K α radiations, its X-ray wavelength is 0.154056nm, and pipe pressure be 40kv, Guan Liuwei 150mA, the angle of diffraction be 2 θ=
50~1000, 2 θ sweep speeds are 502 θ of/min, scanning step △ is 0.02o, it is 10 seconds often to walk the sampling time.In above-mentioned condition
Under, measure single crystalline Si piece surface deposition tetracarboxylic acid dianhydride X-ray diffractogram, i.e. Fig. 3；As can be seen from the figure：Monocrystalline
The tetracarboxylic acid dianhydride of Si pieces surface deposition only has α-PTCDA mutually to exist, and is monoclinic structure；And eliminate depositing for β phases
Homotype hetero-junctions is formd at the interface of, tetracarboxylic acid dianhydride film and Si pieces, there is Characteristics of Schottky Barrier, in the potential barrier
There are electric field and potential.
3rd, ITO nesa coating, its thickness are deposited using the method for sputtering on the surface of deposited tetracarboxylic acid dianhydride
150nm；And in the purity of its surface sputtering sedimentation 50nm be the high-purity N i films of four nine, then sputtered in Ni film surfaces
The purity of 250nm is high-purity Al films of four nine, and in 150 DEG C of logical H2Microalloying 3 minutes in the alloying furnace of gas.Ni is thin
The effect of film is to prevent Al and ITO（Transparent conductive film of In-Sn oxide）React, prevent Al and O to react to form Al2O3,
Improve the stability and reliability of the photodetector.In addition, bottom surface and P-Si rear-face contacts is Au films, pass through micro- conjunction
Aurification processing, makes the device form good low-resistance Ohm contact layer, is conducive to the raising of device photoelectric performance.
4th, the AlNi electrode lead holes of 50 μm of φ are etched and in each core using microelectronics planar technology photolithography method
The edge of the ITO nesa coating of piece makes the step that width is 30 μm, bottom is tetracarboxylic acid dianhydride surface by lithography；So as to
Improve the breakdown reverse voltage of this device and further reduce dark current.Photoetching is that a kind of printing image is mutually tied with chemical attack
The integrated technology of conjunction.Particularly retain 50 μm of Al-Ni electrode lead holes in the surface etch of ito thin film, and etch and go
Except making the surface state of ITO films not change after unnecessary Al-Ni films, there is highly important meaning to the electrical property of device
Justice.
In photoetching process：Using positive photoresist, corresponding supporting have positive photoresist dilution, positive photoresist development
Liquid and positive photoresist go film liquid；Utilize ultraviolet hard mask contact exposure.In a lithographic process, the configuration of photoresist is very
It is important.The resistance to corrosion that it should have, while but also with high-resolution.For this reason, we choose following formula：In darkroom red light
Under, 10g positive photoresists are dissolved in 150ml positive photoresist dilutions, is sufficiently stirred with clean glass bar and is allowed to completely molten
Solution, and in camera bellows stand 24 it is small when after, using hole after 5 μm of sand core funnel is filtered using attraction method be made configure just
Property photoresist, be fitted into dark-coloured ground glass stoppered bottle preserve at normal temperatures it is stand-by.
The total figure of reticle is as shown in figure 4, in Fig. 4：Symbol "+" represents mask graph in a lithographic process and substrate figure
The coordinate of accurate fitting；Mask graph square length of side a is 3000 μm, and etching step width b is 30 μm, Al-Ni contact conductors
The spacing c of bore edges and ito film left end is 170 μm, and Al-Ni contact conductor bore dias d is 50 μm, Al-Ni electrode lead holes
The spacing e of edge and ito film upper end is 1445 μm.
Photoetching concretely comprises the following steps：
4.1 Substrate treatments are low at a temperature of 80 DEG C in an oven to dry 30 minutes；
4.2 gluings, configuration positive photoresist is applied in Al film surfaces；
4.3 front bakings, are baked 30 minutes at a temperature of 150 DEG C in an oven；
4.4 exposures, expose according to common process；
4.5 development；According to common process positive photoresist developing liquid developing；
4.6 rinsing；Rinsed according to common process
Dried after 4.7,100 DEG C, 20 minutes of post bake；
4.8 are etched using lithography layout using normal photolithographic process in the edge of each chip I TO nesa coatings
Go out the step that width is 30 μm；
4.9 use dedicated potassium permanganate corrosive liquids, which can retain the AlNi electrodes with 50 μm of photoresist φ
Lead hole pattern, and the AlNi alloy firms outside AlNi electrode lead holes are corroded to clean, the ito thin film obtained after corrosion
Surface it is straight and even, it is bright, do not produce any stain；
4.10 go film liquid to remove the photoresist after photoetching corrosion in contact conductor hole pattern using positive photoresist；
The preparation method for the configuration positive photoresist that step 4.2 uses is：Under the red light of darkroom, by 10g positive photoresists
150ml positive photoresist dilutions are dissolved in, is sufficiently stirred with clean glass bar and is allowed to be completely dissolved, and 24 are stood in camera bellows
After hour, using hole after 5 μm of sand core funnel is filtered using attraction method, configuration positive photoresist is obtained, will be configured just
Property photoresist be fitted into dark-coloured ground glass stoppered bottle preserve at normal temperatures it is stand-by；
The configuration potassium permanganate that step 4.9 uses corrodes liquid and preparation method thereof：By 3 grams of potassium permanganate and 1 gram of sodium hydroxide
Add in 100ml deionized waters and mix to uniform, obtain configuration potassium permanganate corrosive liquid；The corrosive liquid is maintained around fairlead
Burr is not produced, improving the proof voltage of device and can reduce dark current；At the same time also extend electrically conducting transparent ito film by
Light area, makes photoelectric conversion efficiency be improved；Maintain and burr is not produced around fairlead, improve the proof voltage of device
Performance simultaneously reduces dark current；The light-receiving area of electrically conducting transparent ito film is also extended at the same time, is put forward photoelectric conversion efficiency
It is high.
5th, the above-mentioned tetracarboxylic acid dianhydride chip for being carved with electrode lead hole, under the microscope scribing are formed into 9mm2Core
Piece, 9mm2Chip and GaAs infrared light-emitting diodes chip the metal of circular top end opening is fixed on the method for thermal compression welding
On the stem of shell, and cured with high transparency epoxy encapsulation, its action principle is as shown in Figure 1.
Claims (2)
1. a kind of manufacture method of tetracarboxylic acid dianhydride organic layer photo-coupler, it is characterised in that carry out as steps described below：System
Make Au-Si ohmic contact layers, in Si pieces front deposition tetracarboxylic acid dianhydride film, deposition ito film, high-purity N i films and high-purity Al
The edge of film, etching Al-Ni electrode lead holes and each chip is to etch width as 30 μm of step, thermal compression welding
Tetracarboxylic acid dianhydride chip and GaAs infrared light-emitting diode chips；Specific method is as follows：
A, Au-Si ohmic contact layers are made
By 350 μm of thickness, 2 Ω cm of resistivity, the indices of crystallographic plane 100, the p-type single crystalline Si piece of great circle plate shape, after polished
As substrate, cleaning treatment is carried out：Toluene, carbon tetrachloride, acetone, each ultrasonication 5min of absolute ethyl alcohol are used successively, then
Use deionized water rinsing；Through H2SO4Boil after 3min is cooled to room temperature again with a large amount of deionized water rinsings；Through H2O：HF's
Volume ratio is 9：1 corrosive liquid microprocessor 15 seconds, after repeatedly being rinsed with deionized water again, is dried under infrared lamp；Use fixture
The Si pieces are placed in high vacuum heating coating equipment, treat vacuum up to 5 × 10-3During Pa, in Si in high vacuum vapor deposition room
After the Au films of the back side evaporation 200nm of piece, and lead to H in alloying furnace2Gas, constant temperature 6 minutes, shape at a temperature of 385 DEG C
Into Au-Si ohmic contact layers；
B, in Si pieces front deposition tetracarboxylic acid dianhydride film
Under high vacuum state, the film by tetracarboxylic acid dianhydride in 450 DEG C of its sublimation point to Si pieces front deposition 100nm, makes
With the x-ray powder diffraction instrument of model Rigaku-D/max-2400；Using Cu target K α radiations, its X-ray wavelength is
0.154056nm, pipe pressure are 40kV, and Guan Liuwei 150mA, 2 θ of the angle of diffraction are 50~1000, sweep speed 50/ min, scanning step
For 0.020, it is 10 seconds often to walk the sampling time；Under these conditions, the tetracarboxylic acid dianhydride in single crystalline Si piece surface deposition is measured
Only α-PTCDA mutually exist, i.e., tetracarboxylic acid dianhydride forms monoclinic structure in the clean surface of single crystalline Si piece；Monoclinic system
Structure and the interface of Si pieces form homotype hetero-junctions；
C, ito film, high-purity N i films and high-purity Al films are deposited
It is sequentially depositing ito film, high-purity N i films, high-purity Al films respectively on the surface of deposited tetracarboxylic acid dianhydride film；
The effect of Ni films is to prevent Al from reacting with ITO, prevents Al and O to react to form Al2O3, improve the photo-coupler
Stability and reliability；Wherein the thickness of ITO nesa coating is 150nm；The thickness of Ni films is 50nm；The thickness of Al films
For 250nm；The substrate is in 150 DEG C of logical H2The substrate of 3 minutes obtained six layer structures of microalloying in the alloying furnace of gas；
D, Al-Ni electrode lead holes are etched with the edge of each chip to etch width as 30 μm of step
The AlNi electrode lead holes of 50 μm of φ are etched using microelectronics planar technology photolithography method, and in each chip
The edge of ITO nesa coating makes the step that width is 30 μm, bottom is tetracarboxylic acid dianhydride surface by lithography；Photoetching process
In：Using positive photoresist, corresponding supporting have positive photoresist dilution, positive-tone photo glue developing solution and positive photoresist to go
Film liquid；
Utilize ultraviolet hard mask contact exposure；Concretely comprise the following steps：
D.1 Substrate treatment is low at a temperature of 80 DEG C in an oven to dry 30 minutes；
D.2 gluing, configuration positive photoresist is applied in Al film surfaces；
D.3 front baking, is baked 30 minutes at a temperature of 150 DEG C in an oven；
D.4 expose, exposed according to common process；
D.5 develop, according to common process positive photoresist developing liquid developing；
D.6 rinse, rinsed according to common process；
D.7 dry afterwards, post bake 20 minutes at 100 DEG C；
D.8 width is etched in the edge of each chip I TO nesa coatings using normal photolithographic process using lithography layout
Spend the step for 30 μm；
D.9 dedicated potassium permanganate corrosive liquid is used, which can retain the AlNi contact conductors with 50 μm of photoresist φ
Hole pattern, and the AlNi alloy firms outside AlNi electrode lead holes are corroded to clean, the table of the ito thin film obtained after corrosion
Face is straight and even, it is bright, do not produce any stain；
D.10 film liquid is gone to remove the photoresist after photoetching corrosion in contact conductor hole pattern using positive photoresist；
E, thermal compression welding tetracarboxylic acid dianhydride chip and GaAs infrared light-emitting diode chips
By the above-mentioned tetracarboxylic acid dianhydride substrate for being carved with electrode lead hole, scribing under the microscope forms 9mm2Chip, 9mm2's
The metal shell that chip and GaAs infrared light-emitting diodes chip are fixed on round tip opening with the method for thermal compression welding is drawn
On terminal, and cured with high transparency epoxy encapsulation.
A kind of 2. manufacture method of tetracarboxylic acid dianhydride organic layer photo-coupler as claimed in claim 1, it is characterised in that：Step
The preparation method of the rapid configuration positive photoresist d.2 used is：Under the red light of darkroom, 10g positive photoresists are being dissolved in 150ml just
Property photoresist dilution, be sufficiently stirred with clean glass bar and be allowed to be completely dissolved, and in camera bellows stand 24 it is small when after, use
After the sand core funnel that 5 μm of aperture is filtered using attraction method, configuration positive photoresist is obtained, configuration positive photoresist is loaded
Preserved at normal temperatures in dark-coloured ground glass stoppered bottle stand-by；D.9, the dedicated potassium permanganate that step uses corrodes liquid and preparation method thereof：
3 grams of potassium permanganate are added in 100ml deionized waters with 1 gram of sodium hydroxide and are mixed to uniform, it is rotten to obtain dedicated potassium permanganate
Lose liquid.
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| CN2578985Y (en) * | 2002-08-28 | 2003-10-08 | 兰州大学 | Organic-inorganic heterojunction photoelectric detector |
| CN202094178U (en) * | 2011-03-17 | 2011-12-28 | 甘肃联合大学 | Low-resistance ohmic electrode chip for PTCDA/P-Si heterojunction photoelectric detector |
| CN102723321A (en) * | 2012-07-03 | 2012-10-10 | 黄伟鹏 | Photoelectric coupler lead frame and photoelectric coupler |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN2578985Y (en) * | 2002-08-28 | 2003-10-08 | 兰州大学 | Organic-inorganic heterojunction photoelectric detector |
| CN202094178U (en) * | 2011-03-17 | 2011-12-28 | 甘肃联合大学 | Low-resistance ohmic electrode chip for PTCDA/P-Si heterojunction photoelectric detector |
| CN102723321A (en) * | 2012-07-03 | 2012-10-10 | 黄伟鹏 | Photoelectric coupler lead frame and photoelectric coupler |
Non-Patent Citations (1)
| Title |
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| 《有机/无机光电探测器的研制及电参数优化》;何锡源;《兰州大学硕士学位论文》;20030501;54-55页，图4.1 * |
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