CN1143400C - Organic diodes with switchable photosensitivity - Google Patents

Organic diodes with switchable photosensitivity Download PDF

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CN1143400C
CN1143400C CNB988091038A CN98809103A CN1143400C CN 1143400 C CN1143400 C CN 1143400C CN B988091038 A CNB988091038 A CN B988091038A CN 98809103 A CN98809103 A CN 98809103A CN 1143400 C CN1143400 C CN 1143400C
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photodiode
voltage
array
electrode
luminous sensitivity
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CN1270706A (en
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俞钢
曹镛
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DuPont Displays Inc
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Uniax Corp
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Abstract

Organic diode detectors (10) with switchable photosensitivity are achieved using organic photo layers (12) in the photodiodes and a detector circuit (15, 16) which applies a reverse or forward bias voltage across the diodes. These diodes can be arranged in matrices which function as high-performance, two-dimensional image sensors. These image sensors can achieve full color or selected color detection capability.

Description

Switchable organic photoelectric diode detector and application thereof
The present invention relates to organic photoelectric diode and the application in two-dimensional image sensor thereof.The present invention relates to utilize voltage to switch and can be arranged as the organic photoelectric diode of image sensor array of ranks (x-y) matrix form of passive addressable in preferred embodiment more, wherein the organic imageing sensor of x-y addressable (pattern matrix) has full color or selected colored detectability.
The exploitation of pattern matrix photodetector has long history in the device industry.The early stage method of imaging technique comprises the device based on the solid-state material thermal effect.Be based on the photodiode of employing inorganic semiconductor making and the high sensitivity pattern matrix and the matrix of charge-coupled device (CCD) thereafter.
The photodiode that adopts inorganic semiconductor such as silicon to make is represented the light-sensitive device of the high quantum yield of a class.This device is widely used in the visible light detection application always in the past few decades.Yet their photoelectric current voltage response characteristic curve is straight, makes them be difficult to be used for making the passive imageing sensor of high pixel density x-y matrix-addressable." x-y " matrix is first group of electrode and second group of two-dimensional array that electrode is vertical.Work as passive device, as resistance, diode or liquid crystal cell, during as the pixel cell at intersection point place, this matrix often be called " passive " matrix (with adopt active device, as thin-film transistor, " active " matrix of connection of controlling each pixel is relative).
For row from passive matrix and column electrode effectively to each pixel cell addressing, pixel cell must show very strong non-linear current voltage (" I-V ") characteristic or with the I-V relation of threshold voltage.This requirement can be to be used light-emitting diode or liquid crystal cell to construct passive x-y addressable display to provide the foundation.Yet, since the photoresponse of inorganic photodiode be anti-(to) bias voltage dependent form, it is unpractiaca that the photodiode of being made by the inorganic semiconductor crystal is used for the passive imageing sensor of high pixel density, crosstalking between the pixel is too many.For avoiding crosstalking, existing two-dimensional array of photodiodes of being made by inorganic photodiode must be made each pixel independent wiring, the operation that this is time-consuming and cost is high.In the occasion of this independent wiring, the number of I/O lead is proportional to the number of pixel.Because the difficulty of manufacturing and plate intraconnections, the number of commercially available two-dimensional array of photodiodes pixel is limited to≤16 * 16=256.Representative commercially available photodiode array comprises SiemensKOM2108 5 * 5 photodiode arrays and Hamamatsu S3805 16 * 16 Si photodiode arrays.
The exploitation of CCD provides another solution at the high pixel density two-dimensional image sensor.Ccd array is an integrated device.They are different with x-y addressable passive matrix array.The operation principle of CCD relates to the sequential transfer of electric charge from a pixel to one other pixel.Shift between this pixel and repeat to take place and cause charge migration, finally arrive array edges for reading.These device application very lagre scale integrated circuit (VLSIC) (" SLIC ") technology and require in its manufacture process, to reach the perfection of extreme height.This makes the ccd array (CCD value～＄ 10 of 0.75 " 1 " size that involves great expense 3-10 4) and make the size of commercially available CCD product be limited to inferior inch size.
Originally be that what to need to develop for LCD is that thin-film transistor (" the TFT ") technology of substrate can provide active matrix substrate to be used for making the organic imageing sensor of large-sized x-y addressable with glass or quartz.Amorphous silicon (a-Si) the p-i-n photocell large scale full-color image-position sensor that employing is made on amorphous silicon (a-Si) TFT plate has displaying [R.A.Street recently, J.Wu, R.Weisfield, S.E.Nelson and P.Nylen, Spring Meeting ofMaterials Research Society, San Francisco, April 17-21 (1995); J.Yorkston et al., Mat.Res.Soc.Sym.Proc.116,258 (1992); R.A.Street, Bulletin of Materials Research Society 11 (17), 20 (1992); On the other hand, E.Antonuk and R.A.Street, U.S.Patent No.5,262,249 (1993); R.A.Street, U.S.Patent No.5,164,809 (1992)].Follow the development in the CMOS technology with submicron resolution, parallel effort based on the small size active pixel optical sensor aspect of the CMOS technology on the silicon chip reactivates independently [about latest developments referring to Eric J.Lerner, Laser Focus World 32 (12) 54,1996].This CMOS technology is allowed that photocell and drive circuit and timing circuit are integrated and is realized the monolithic image video camera.
CCD, a-Si TFT and the existing/emerging solid state image sensor technology of active pixel cmos image sensor representative.Yet, expend highly because make the related technology of these most advanced and sophisticated devices, its application is severely limited.In addition, in manufacturing process, use the SLIC technology that commercially available CCD and active pixel cmos sensor are limited to inferior inch device size.
The photodiode that adopts organic semiconductor to make is represented the novel optical sensor of a class, and its course of processing has up-and-coming advantage.Though once had in early days about adopting organic molecule and conjugated polymer to make the report of photodiode in the eighties, but observed photoresponse is very little [about the commentary of the early stage work of organic photoelectric diode referring to G.A.Chamberlain, Solar Cells 8,47 (1983)].Adopting conjugated polymer aspect active material, to get along with in the nineties; Referring to, such as, the report of following photoresponse about PPV (polyhenylene inferior ethene) and derivative thereof: S.Karg, W.Riess, V.Dyakonov, M.Schwoerer, Synth.Metals 54,427 (1993); H.Antoniadis, B.R.Hsieh, M.A.Abkowitz, S.A.Jenekhe, M.Stolka, Synth.Metals 64,265 (1994); G.Yu, C.Zhang, A.J.Heeger, Appl. Phys.Lett.64,1540 (1994); R.N.Marks, J.J.M.Halls, D.D.D.C.Bradley, R.H.Friend, A.B.Holmes, J.Phys.:Condens.Matter 6,1379 (1994); R.H.Friend, A.B.Homes, D.D.C.Bradley, R.N.Marks, U.S.Patent No.5,523,555 (1996)].Recently progress shows that the luminous sensitivity of organic photoelectric diode can be improved when applying reverse bias.Once observing luminous sensitivity in the ITO/MEH-PPV/Ca thin-film device under 10V reverse bias (430nm) is approximately～90mA/Watt, be equivalent to quantum efficiency＞20%el/ph[G.Yu, C.Zhang and A.J.Heeger, Appl.Physy.Lett.64,1540 (1994); A.J.Heeger and G.Yu, US Patent5,504,323 (April 2,1996)].In the photodiode that adopts poly-(3-octyl group thiophene) to make, can be observed luminous sensitivity when applying-15 V bias voltages in most of visible light district above 0.3A/Watt.
Luminous sensitivity in the organic semiconductor can shift by the excitation state electric charge and be improved; Such as utilizing acceptor, as C 60Or derivatives thereof makes semi-conducting polymer sensitization [N.S.Sariciftci and A.J.Heeger，US Patent 5,331,183(July 19，1994)；N.S。Sariciftci and A.J.Heeger，US Patent 5,454,880(Oct 3，1995)；N.S.Sariciftci，L.Smilowitz，A.J.Heeger and F.Wudl，Science 258,1474(1992)；L.Smilowitz，N.S.Sariciftci，R.Wu，C.Gettinger，A.J.Heegrand F.Wudl，Phus.Rev.B 47,13835(1993)；N.S.Sariciftci and A.J.Heeger，Intern.J.Mod.Phys.B 8,237(1994)]。Quantity of photogenerated charge shifts and can prevent early stage compound and stable charging separation, thereby improves for the charge carrier quantum yield [B.Kraabel, the C.H.Lee that compile thereafter, D.McBranch, N.S.Sariciftci, D.Moses and A.J.Heegr, Phys.Rev.Lett.213,389 (1993); B.Kraabel, D.McBranch, N.S.Sariciftci, D.Moses and A.J.Heegr, Phys.Rev.B 50,18543 (1949); C.H.Lee, G.Yu, D.Moses, K.Pakbaz, C.Zhang, Sariciftci, A.J.Heegr, and F, Wudl, Phys.Rev.B.48,15425 (1993)].By using the charge transfer mixture as the light-sensitive material in the photodiode, can under low reverse bias, obtain the outer luminous sensitivity of 0.2-0.3A/W and the quantum yield [G.Yu of 50-80%el/ph at 430nm, J.Gao, J.C.Hummelen, F.Wudl and A.J.Heegr, Science 270,1789 (1995)].On same wavelength, the luminous sensitivity that ultraviolet strengthens silicon photoelectric diode is～0.2A/W, with bias voltage irrelevant [S.MHz.Sze, Physics of SemiconductorDevices (Wiley, New York, 1981) Part 5].Like this, use the luminous sensitivity of the photodiode of polymer charge transmission mixture making to compare with the luminous sensitivity of the photodiode that uses organic semiconductor crystal to make.Except its high luminous sensitivity, this organic photoelectric diode shows very big dynamic range; Report claims its luminous sensitivity from 100mW/cm 2Drop to nW/cm 2, straight relatively in the time of promptly between 8 number order magnitude range [G.Yu, H.Pakbaz and A.J.Heeger, Appl.Physy.Lett.64,3422 (1994); G.Yu, J.Gao, J.C.Hummelen, F.Wudl and A.J.Heeger, Science 270,1789 (1995); G.Yu, and A.J.Heeger, Appl.Physy.78,4510 (1995)].The polymer photodiode can at room temperature move, and luminous sensitivity only reduces 1/2[G.Yu from room temperature to 80 K to the operating temperature relative insensitivity, H.Pakbazand A.J.Heegr, Appl.Physy.Lett.64,3422 (1994)].
The situation of polymer light-emitting device identical [G.Gustafsson, Y.Cao, G.M.Treacy, F.Klavetter, N.Colaneri, and A.J.Heeger, Nature 357,477 (1992); A.J.Heeger and J.Long, Optics ﹠amp; Photonics News, Aug.1996, p.24], at room temperature can produce large tracts of land high sensitivity polymer photodiode by solution-treated, they can be made becomes special shape (for example on hemisphere to combine with optical element or optical system), or can make soft or folding form.Processing advantage also makes and optical sensor directly can be produced on the optical fiber.Similarly, the organic photoelectric diode can with optics or electronic device, as the integrated circuit on the silicon chip, mixing manufacture.These characteristics make the organic photoelectric diode be specially adapted to a lot of new application.
We are for finding new application by the luminous sensitivity that applies in the reverse bias enhancing organic photoelectric diode.
We find that this variable luminous sensitivity can be used to the optical sensor of realizing that switching voltage switches.When applying reverse bias (normally greater than 1V, and more commonly in the 2-15V scope), photodiode can be by greater than 1mA/W, particularly 10-500mA/W or 30-300mA/W, luminous sensitivity connect.To hang down several orders of magnitude near the voltage of interior (intrinsic) current potential luminous sensitivity down, equal output zero of 8-16 bit digital reading circuit.This nearly nought state just can be defined as the off-state of photodiode.
This organic photoelectric diode that utilizes voltage to switch can be used as the single pixel in the passive diode array.The form of this array can be that anode passes through the x-y addressable array that row (row) electrode connects and negative electrode connects by row (OK).Each pixel all can be selected, and the information on each pixel all can be read and can not be crosstalked.
This array can utilize with adopting soluble semiconductive conjugated polymer (and/or its matrix polymer) and make the processing advantage that organic diode structure is associated.This material layer can be become so that make big active region on the substrate of required form by solution casting.This also makes the active region can make flexible form.These light active materials can utilize photographic printing, the microcontact printing, and methods such as shadow mask form figure on the even substrate of optics.Can be opaque for the optical sensor substrate that is applied in the application of visible light sensing to the light of λ＜400nm, thus make pixel insensitive to ultra-violet radiation.
Employed photoactive layer is made by organic material in this switchable photodiode.They can have various forms.They can be conjugation semi-conducting polymer and the high polymer mixture that comprises this material.Also can adopt the conjugated polymer D-A mixture that has as donor and polymer and monomeric acceptor, the same with molecule donor known in the field (being molecule rather than big molecule) with acceptor.The latter's example comprises anthracene and derivative thereof, pinacyanole (pinacyanol) and derivative thereof, thiophene oligomers (as own thiophene, 6T and hot thiophene, 8T) and derivative or the like, phenyl oligomer (as sexiphenyl or hot benzene) or the like.In addition, can also use the organic semiconducting materials of the donor/acceptor heterojunction configuration of multilayer.
Organic imageing sensor provided by the present invention can have monochrome or polychrome measuring ability.In this imageing sensor, colored selection can by will suitable color filter plate and organic imageing sensor reach the image sensor array of having described and combine and reach.As needs, color filter plate can be used as the substrate of load image transducer.
In addition, embodiments of the invention can provide the organic imageing sensor with full color measuring ability.In this organic imageing sensor, color filter plate is by redness, and green and blue color filter constitute, and their graphical format is consistent with the form of photodiode array.Color filter plate and the photodiode array that is made of graphical filter is connected to each other (and cooperation) and forms color image sensor.The color filter plate that graphical colour filter constitutes can directly be used as the substrate of imageing sensor.
Full color detects also can utilize the spectral response cut-off wavelength to be 500nm, and three kinds of photodiodes of 600nm and 700nm detect the RGB look respectively and reach.Differentiating in the reading circuit can be extracted redness (600-700nm), green (500-600nm) and blue (400-500nm) signal.
These organic photoelectric diodes except being applied to their intrinsic response spectrum district (usually at 200nm-1000nm), also can be used for other spectral regions, and as ultraviolet, X ray and infrared spectral region carry out light sensing.The light sensing that carries out photon energy outside its intrinsic spectral regions can be by the conversion up and down of energy and is reached.Can be such as, the light sensing in ultraviolet and X ray spectral regions by between ultraviolet or x-ray source and optical sensor, fluorescence coating being set or flash layer reaches.This layer will be converted to visible light to high-energy radiation and be arrived by organic light sensors.Infrared radiation and high energy particle radiation can detect according to similar principles.
The radiation of these organic optical sensors specific wavelength in the ray spectrum district to deep ultraviolet and when needing also has intrinsic sensitiveness.These wavelength and corresponding photon energy thereof are relevant with idle molecular orbit (LUMO) or the conduction band bottom minimum from interior nuclear energy level (can be with) optical transition to energy.
Below with reference to the accompanying drawings the present invention is illustrated, in the accompanying drawing:
The schematic sectional view that Fig. 1 is assemblied in the circuit for voltage switches light electric diode 10 of the present invention.Photoelectric current can be read by the ammeter that is inserted in the loop;
Fig. 2 is the schematic sectional view of voltage switches light electric diode 20 of the present invention, and the structure that the configuration of wherein reversing is represented has a transparency electrode that contacts with the Free Surface of active layer;
Fig. 3 is the decomposing schematic representation of the 2D imageing sensor 30 that is made of the x-y addressable passive matrix of voltage switches light electric diode;
The decomposing schematic representation of the full-color image-position sensor 40 that the x-y addressable photodiode array that Fig. 4 is connected with color filter plate for utilization constitutes;
Fig. 5 is the decomposing schematic representation that utilizes the full-color image-position sensor 50 that x-y addressable photodiode array constitutes, and wherein each full color pixel all is by having different cut-off wavelengths, as 700nm, 600nm and 500nm, three kinds of light-sensitive materials make;
Fig. 6 is the photoelectric current in the ITO/MEH-PPV/Ca device and the graph of relation of bias voltage;
Fig. 7 is the transmission characteristic figure of PANI-CSA and PEDT-PSS conductive polymer electrodes; The eye response curve V (λ) of human eye also is shown among the figure.
Fig. 8 is the photoelectric current (circle) of ITO/MEH-PPV:PCBM/Al photodiode and the curve chart of dark current (square).Photoelectric current is to be～10mW/cm in intensity 2White light down measure,
Fig. 9 is the ITO/P3OT/Au photodiode in dark (circle) and at～10mW/cm 2The lighting condition of 633nm under the current-voltage characteristic curve figure of (square);
Figure 10 between the column electrode of 7 * 40 photodiode arrays and row electrode at dark (line) and (circle) records under the room lighting situation I-V performance diagram;
Figure 11 is the type of drive schematic diagram of 7 * 40 photodiode arrays.To utilize the changeable photodiode of ITO/MEH-PPV:PCBM/Ag to describe.
Figure 12 is the photoresponse curve figure by the voltage switches light electric diode of P3OT making;
Figure 13 (a) is the photoresponse curve figure of the voltage switches light electric diode of spectral response simulations THE SPECTRAL RESPONSE OF THE HUMAN EYE V (λ);
The transmissivity that Figure 13 (b) filters mating plate for long-pass reaches and the corresponding eye response V of Figure 13 (a) (λ) curve chart;
Figure 14 under-2V, work day blind UV-detector spectral response curve figure.Be depicted in the MEH-PPV:C on the ITO/ glass substrate simultaneously 60The photoresponse that the photoresponse of photodiode and ultraviolet strengthen the Si photodiode is with making comparisons;
The response curve of Figure 15 (a) PTV photodiode;
Figure 15 (b) R that the PTV photodiode that is connected with color filter plate constitutes that serves as reasons, G, the photoresponse curve figure of B photodiode;
The transmittance graph figure of Figure 15 (c) employed colour filter when being drawn on data among Figure 15 (a) and 15 (b) in generation;
Figure 16 (a) is by PPV (opening square), the normalization spectral response curve figure of the photodiode that PDHPV (opening circle) and PTV (filled circles) make;
Figure 16 (b) is the redness that is derived by the response of the diode among Figure 16 (a), green and blue detection curve chart;
Figure 17 is illustrated in the dark and the I-V response curve of PPV photodiode under lighting condition;
Figure 18 is illustrated in the dark and the I-V response curve of photodiode under lighting condition; Photoactive layer wherein is the donor/acceptor double-decker.
The invention provides a kind of highly sensitive photodiode that voltage switches luminous sensitivity that has; Its luminous sensitivity can utilize selected voltage to switch, thereby crosstalking in this voltage switches light electric diode can be reduced to acceptable level. This changeable photodiode is made two dimension (2D) the passive images sensor of (x-y) addressable performance that has ranks. Voltage switches light electric diode adopts metal-semiconductor-metal (M-S-M) membrane structure, wherein adopts organic film, such as semiconducting polymer film or high polymer mixture, as light active material. Detect or polychrome detects and can realize by imageing sensor is connected on the optical colour filter at the selected look of visible light and ultraviolet light scope. Red, green, blue (R, G, B) and full-colour image manufacturing of the fiber grating sensors process be that x-y addressable organic polymer diode matrix is connected with RGB (RGB) color filter plate, or make at the even substrate of optics and to have the photoresponse cutoff wavelength respectively at the photodiode of 500nm, 600nm and 700nm.
As seen blind (visible-blind) or day blind (solar blind) ultraviolet detect and can utilize and have light slit＞3.1eV (light active material of wavelength＜400nm), or the organic optical sensor by will having little light slit with lead to optical light filter at the opaque ultraviolet band of visible region and be combined and carry out. Except the light sensing in visible and ultra-violet (UV) band (200nm-400nm), in other spectral regions, as at deep ultraviolet, can realize by organic optical sensor is combined with fluorescence coating or flash layer at X ray with at the light sensing of infrared region. High-energy radiation or infra-red radiation can be exchanged into visible radiation and are detected by organic photodetector. Radiation at the specific wavelength of deep ultraviolet and X ray spectral regions also can directly utilize these organic photodiodes to detect. These wavelength are corresponding with the bottom of idle molecular orbit (LUMO) from interior nuclear level (can be with) optical transition to minimum energy or conduction band.
The voltage switch photodiode makes the 2D imageing sensor become possibility. Utilize this kind photodiode as the sensing element in the ranks matrix, in the time of just can being configured to work without the 2Dx-y addressable passive images sensor of crosstalking. Because luminous sensitivity and voltage is in close relations, just can select row in the 2D photodiode array and utilize suitable bias voltage that it is connected, and the rest of pixels on other row is insensitive to incident light. Adopt this method of operation, physical arrangement is the linear diode array that the 2D matrix of the capable N row of M just turns to N isolation approximately, and each has M element; The linear diode array of described isolation is not owing to crosstalking that the limited resistance between the different lines device produces. Adopt this kind 2D passive photoelectric diode matrix just can utilize respectively being listed as and image being read of train of pulse scan matrix. Because the decreased number of contact electrode is to N+M in the x-y addressable matrices, and be N * M in the occasion of single connection, so large scale, highdensity 2D pattern matrix just become practicable (can compare favourably with the high pixel density array of display that utilizes lcd technology to make). For example, for 1000 * 1000 pel arrays, the present invention can reduce to required electrode number original 1/500. This polymeric image sensor array just can provide the 2D image sensing array of the low-cost high pixel density of a kind of unique large tracts of land of manufacturing under room temperature or low temperature.
As example is shown herein, the spectral response of polymeric image sensor can cover with relatively straight response curve whole visible light. The part of this visible spectrum also can utilize bandpass filter or low pass filter to select. Detect by imageing sensor is connected the polychrome that to realize visible light and ultra-violet (UV) band with color filter plate. The description of the manufacture process of full-colour image sensor is to utilize x-y addressable polymer diode matrix and RGB color filter plate.
Definition and device architecture
Description at preferred embodiment neutralizes in the claims, will quote the term of several definition. One group of term relates to the structure of voltage switches light electric diode. The cutaway view of the switches light of voltage shown in Fig. 1 electric diode. Voltage switches light electric diode 10 adopts metal-semiconductor-metal (M-S-M) structure of thin film device. Specifically, device 10 comprises:
The formation of " photosensitive layer " (layer 12) is an organic semiconducting materials, as conjugated polymer, and high polymer mixture, polymer/molecule high polymer mixture, molecule organic layer or organic mixture layer; Or in conjunction with the sandwich construction of above-mentioned material;
Two " contact electrode " (layer 11,13) is as anode and the negative electrode of extracting the photodiode in electronics and hole respectively from photoactive layer out.One (layer 11 among Fig. 1) in the electrode is made into transparent or semitransparent, and tolerable incident light 18 is absorbed in active layer (12).
The definition of " anode " electrode is the electric conducting material with work function higher than " negative electrode " material.
Be shown in Fig. 1 respectively, in the device 10,20,30,40 and 50 in 2,3,4 and 5, electrode 11 is identical with the relation of layer 12 and light source 18 (or 18 ') with 13.
As illustrated in fig. 1 and 2, electrode 11 with 13 respectively by lead 17 and 17 ' be connected with grid bias power supply 15.Detector 16 is series at the photoresponse that original measuring light electric diode generates incident light 18 responses in this circuit.All devices in Fig. 1-5 can use same circuit in (10,20,30,40 and 50).
Device also can comprise optional substrate or sheet base 14 as shown in Figure 5.This is a kind of solid rigidity or soft thin layer, is to be used for providing robustness for the matrix array of diode and/or diode.When light during from substrate side incident, substrate should be transparent or semitransparent.Normally used is glass, polymer flake or soft plastic films.Be transparent broadband semiconductor disk (as SiC, SiN) below its optical band gap, also can use in some cases.In these occasions, doped region also can be used as contact electrode 11.
Also can use the device of geometry counter-rotating shown in Figure 2 in the application.In this configuration, light 18 is from the incident of " back of the body " electrode side, and can adopt opaque material as backing material.Such as, by using organic semiconductor disk (as silicon chip) as substrate 14, and the degree by semiconductor doping being reached " conduction " (following this is defined), disk just not only can be used as substrate 14 but also can be used as contact electrode 11.The available advantage of inversion structures be can with optical sensor with directly be made on the inorganic semiconductor substrate driving/reading circuit integrated (utilizing integrated circuit technique) together.
The definition of incident light 18 (or 18 ') normally comprises visible wavelength (400-700nm), ultraviolet wavelength (100-400nm) and infrared wavelength (700-2000nm).Before point out, if be fit to, also can use other wavelength.
Some layers are described to " transparent " or " translucent " layer.These two terms are to be used to refer to material can make the light transmissive character of most of incident that incides on it.Term " transparent " is to be used for describing transmissivity to surpass 50% substrate, and term " translucent " is to be used for describing the substrate of transmissivity between 50% to 5%.
" conduction " layer or conductivity of electrolyte materials are usually greater than 0.1S/cm (west/centimetre).The conductivity of semi-conducting material is 10 -14To 10 -1S/cm.
" just " (or " bearing ") bias voltage refers to the occasion that applies high potential on anode (negative electrode).When referring to negative value, such as applying reverse bias so that the occasion of the luminous sensitivity that is enhanced, with the absolute value representation relative value, that is, such as ,-10V (instead) bias voltage greater than-5V (instead) bias voltage.
The structure of the passive photodiode array of x-y addressable shown in Figure 3 (2D imageing sensor 30).In Fig. 4 is the full-color image-position sensor 40 that utilizes x-y addressable photodiode array to constitute.In these devices, the graphics shape of anode and cathode electrode 11 ', 13 ' normally row is orthogonal with row.In some applications, photoactive layer 12 not necessarily needs graphically.One of the intersection point definition of row-column electrode has and Fig. 1 or similar device architecture shown in Figure 2.Row-column electrode 11 ', 13 ' limits the active region of each pixel.
Color filter array 19 (each pixel of colour filter comprises RGB colour filter 19 ') is connected with the photodiode display panel.Can adopt for this purpose and be similar to the employed colour filter that separates in Color Liquid Crystal Display [seeing about its summary: M.Tani and T.Sugiura, Proceedings of SID, Orlando, Florida (1994)].In a better preferred embodiment, color filter plate can directly be coated on the substrate of photodiode array.One group of transparency electrode 11 (such as constituting) by ITO (tin indium oxide) can be produced on the colour filter coating above.In this configuration, can reach high pixel density with micrometer-class size.
Adopt another scheme 50 shown in Figure 5 can accomplish panchromatic detection.In this scheme, each panchromatic pixels 12 ' comprise three photodiode 12R, 12G and 12B have long wave cut-off function wavelength 700,600 and 500nm respectively.These photodiodes are produced in definite zone of substrate by three kinds of light-sensitive materials.Active layer graphically can utilize photoetching, silk screen printing, methods such as shadow mask are finished.Correct red-green-blue color information can be by to from three sub-pixels, and 12R, the signal of 12G and 12B (in reading circuit) carry out differential and obtain, can be referring to example of the present invention.Usually the optics homogeneous material as substrate is transparent at visible region, and opaque at ultraviolet region.
Photoactive layer
Photoactive layer 12 in voltage switches light electric diode is made by the thin layer of organic semiconducting materials.Active layer can comprise one or more semiconductive conjugated polymers, independent inclusive NAND conjugation material, one or more organic molecules, or oligomer.Active layer can be the mixture with two or more conjugated polymers of similar or different electron affinities and electron energy band width.The latter's special advantage is that the different electron affinities of component can cause quantity of photogenerated charge to shift and separation of charge; A kind of phenomenon [N.S.Sariciftci and A.J.Heeger, US Patent 5,331,183 (July 19,1994) that strengthens luminous sensitivity; N.S.Sariciftci and A.J.Heeger, US Patent 5,454,880 (Oct 3,1995); N.S.Sariciftci, L.Smilowitz, A.J.Heeger and F.Wudl, Science 258,1474 (1992); L.Smilowitz, N.S.Sariciftci, R.Wu, C.Gettinger, A.J.Heegr and F.Wudl, Phus.Rev.B 47,13835 (1993); N.S.Sariciftci and A.J.Heegr, Intern.J.Mod.Phys.B 8,237 (1994)].As mentioned above, this active layer also can be a series of heterojunction (heterojunction) that utilize organic material or mixture.
The film of organic molecule oligomer and molecule mixture can utilize thermal evaporation, and methods such as chemical vapor deposition (CVD) are made.Conjugated polymer, polymer/poly-mixture, the film of polymer/oligomer and polymer/molecule mixture often can be by directly being poured into a mould by the solution that adopts usual vehicle or utilizing similar fluid to handle mutually and make.When adopting polymer or poly-mixture as active layer, device can directly be made on the soft substrate and form unique engineering properties and be soft optical sensor.
Common semiconductive conjugated polymer is including but not limited to polyacetylene (" PA ") and derivative thereof, polyisothianaphthene and derivative thereof, polythiophene (" PT ") and derivative thereof, polypyrrole (" PPr ") and derivative thereof, poly-(2, the inferior ethene of the inferior thiophene of 5-) (" PTV ") and derivative thereof, p-poly-phenyl (" PPP ") and derivative thereof, poly-fluorenes (" PF ") and derivative thereof, polyphenylene ethylene support (" PPV ") and derivative thereof, polycarbazole and derivative thereof, poly-1, the 6-heptadiyne, poly quinoline (polyquinolene) and semiconductor polyaniline (being colourless emeraldine and/or emeraldine base form).The representative of polyaniline material is at United States Patent (USP) 5,196, description arranged in 144, quotes it herein as a reference.In these materials, handle advantage because of it and preferably adopt the material that is dissolvable in water organic solvent.
Be dissolvable in water the PPV derivative in the ordinary organic solvents, comprise poly-(2-methoxyl group-5-(2 '-ethyl-own oxygen base)-1,4-phenylene vinylene), (" MEH-PPV ") [F.Wudl, P.-M.Allemand, G.Srdanov, Z.Ni and D.McBranch, in Materialsfor Nonlinear Optics:Chemical Prospectives, edited by S.R.Marder, J.E.Sohn and G.D.Stucky (The American Chemical Society, Washington DC, 1991), p.683.], poly-(2-butyl 1-5-(2-ethyl-hexyl)-1,4-phenylene vinylene), (" BuEH-PPV ") [M.A.Anderson, G.Yu, A.J.Heeger, Synth.Metals 85,1275 (1997)], poly-(2, two (the cholestane oxygen bases)-1 of 5-, 4-Asia-phenyl vinylene), (" BCHA-PPA ") [see U.S. Patent application No.07/800,555, quote herein as a reference] or the like.The example of solubility PT comprises poly-(3-alkylthrophene), (" P3AT "), and wherein the chain of alkyl side comprises the carbon more than 4, such as 5 to 30 carbon.
Organic imageing sensor can utilize the poly-mixture of donor/acceptor to make as photoactive layer.These poly-mixtures can be semi-conducting polymer/poly-mixture or the semi-conducting polymer with suitable organic molecule.The example of the donor of donor/acceptor polymer includes but not limited to the conjugated polymer just mentioned, i.e. PPV, PT, PTV, and polyphenylene and soluble derivative thereof.The example of the acceptor of donor/acceptor polymer includes but not limited to paracyanogen base phenylene vinylene (poly (cyanaophenylene vinylene), " CN-PPV ") and derivative thereof, and fullerene molecule is as C 60And functional deriv, and the organic molecule that is used as photoreceptor up to now in the art.
Also can utilize two kinds of Semiconductor Organic thin layers of donor/acceptor heterojunction form to make photoactive layer.In these structures, donor layer is conjugated polymer layer normally, and receptive layers comprises paracyanogen base phenylene vinylene (" CN-PPV "), and fullerene molecule is as C 60And functional deriv such as PCBM and PCBCR, or up to now in the art as the organic molecule of photoreceptor.This heterojunction layer example of structure of photoactive layer is including but not limited to PPV/C 60, MEH-PPV/C 60, PT/C 60, P3AT/C 60, MEH-PPV/C 60Or the like.
This active layer also can be by the broadband polymer, as mixing through dye molecule with the poly N-vinyl carbazole (poly-N-vinylcarbozole, " PVK ") of the luminous sensitivity that strengthens its visible range, makes.At this moment, the broadband organic substance also is used as the transferring material in hole (or electronics) both as the bond of matrix.Its example is including but not limited to PVK/ neighbour-tetrachloroquinone, PVK/ rhodamine B and PVK/ coronene or the like.
Photoactive layer can use organic molecule, oligomer or molecule mixture as photoactive layer.In this embodiment, light-sensitive material becomes film by chemical vapour deposition (CVD), molecule extension or other known thin film deposition fabrication techniques.Suitable material is including but not limited to anthracene, phthalocyanine dye, and 6-thiophene (" 6T "), benzophenanthrene and derivative thereof, as 2,3,6,7,10,11-six hexyl sulphur benzophenanthrenes (hexahexylthiotriphenylene), or molecule mixture such as 6T/C 60, 6T/ pinacyanol, phthalocyanine/neighbour-tetrachloroquinone or the like.This photoactive layer also can be the sandwich construction in conjunction with above-mentioned material.
The example that can be used as organic molecule, oligomer and the molecule mixture of active layer comprises anthracene and derivative thereof, aphthacene and derivative thereof, phthalocyanine dye and derivative thereof, pinacyanol and derivative thereof, fullerene (" C 60") and derivative, thiophene oligomers (as 6-thiophene " 6T " and 8-thiophene " 8T ") and derivative thereof or the like, phenyl oligomer (as 6 phenyl or 8 phenyl) and derivative thereof or the like, 6T/C 60, 6T/ pinacyanol, phthalocyanine dye/neighbour-tetrachloroquinone, anthracene/C 60, anthracene/neighbour-tetrachloroquinone or the like.
In certain embodiments, active layer 12 comprises that one or more organic additives (they are that optics is inactive) are so that the performance of changes and improvements device.The example of these additive molecules comprises anionic surfactant, as has the ether sulfate of common structure.
R(OCH 2CH 2) nOSO 3 -M +
Wherein R represents alkyl alkyllaryl,
M +Represent proton, metal or amine equilibrium ion,
N is the molal quantity of ethylene oxide, usually n=2～40.
Adopt this anionic surfactant as the performance that strengthens polymer LED by Y.Cao show [U.S. Patent application No.08/888, in 316, quote herein as a reference].
Other kinds additive comprises solid electrolyte or organic salt.Example comprises poly(ethylene oxide), trifluoromethayl sulfonic acid lithium or its mixture, DBSA 4-butyl amine or the like.This electrolyte of adding and invention novel light-emitting device illustrate [U.S. Patent application No.08/268,763] by Q.Pei and F.Klavetter in light emitting polymer.
At active layer is when being made of two-phase or multiphase the organic mixture with different electron affinities and optical energy band, receives being separated of (millimicro) level usually, and forms heterojunction in the boundary zone.
Have high electron affinity as electron acceptor, and have low high electron affinity (or low ionization energy) as electron donor.These organic mixtures form a class charge transport material, and make the Process of Charge Separation of photopolymerization initiation define [N.S.Sariciftci and A.J.Heeger, Intern.J.Mod.Phys.B 8,237 (1994)] with following step:
Step 1:D+A → 1,3D *+ A, (D is excited)
Step 2: 1,3D *+ A → 1,3(D_A) *, (concentrating on exciting of D-A)
Step 3: 1,3(D_A) *→ 1,3(D 5-_ A δ-) *, (electric charge shifts and starts)
Step 4: 1,3(D δ_ A δ-) * → 1,3(D-._A -.), (form ion radical to)
Step 5: 1,3(D +._A -.) → D +.+A -., (separation of charge)
Wherein (D) represents organic donor, and (A) represents organic receptor; 1,3 represents single excitation state or three excitation state respectively.
The common thickness of active layer is that hundreds of dusts are to thousands of dusts; Be 300-5000 angstrom unit (1 dust=10 -8Cm).Though the thickness of active film is not crucial, device performance can utilize the optical density (OD) in the interested spectral regions to be improved less than 2 thin film usually.
Electrode
As illustrated in fig. 1 and 2, organic photoelectric diode of the present invention be configured as the M-S-M structure, wherein organic active layer combines with contact electrode in both sides.In configuration shown in Figure 1, transparent substrates 14 and transparency electrode 11 are as a contact electrode.Can use tin indium oxide (" ITO ") as electrode 11.Other transparent electrode material comprises the zinc oxide (" AZO ") of mixing aluminium, mixes the tin oxide (" ATO ") of aluminium, tin oxide or the like.These conductive coatings are made of the metal-oxide compound of mixing, they near ultraviolet to infrared transparent.
Electrode 11 among Fig. 1 (or electrode among Fig. 2 13) can be made of conducting polymer, as utilize polyaniline (polyaniline) in the emeraldine salt of the treatment technology preparation that equilibrium ion induces, this technology is disclosed in U.S. Patent No. 5,232,631 and Appl.Phys.Lett.60,2711 (1992), also can utilize the other technologies preparation.Polyaniline film as electrode can at room temperature be formed by the solution casting with high uniformity.The organic conductive electrode combines the optical sensor that can make complete softness with polymer substrate and organic active layer.The conducting polymer that also can use other is as transparent or semitransparent electrode (13 among 11 among Fig. 1 or Fig. 2), comprise polyvinyl dioxygen base thiophene/poly styrene sulfonate (polyethylenedioxythiophene polystyrene sulfonate, " PEDT/PSS ") [Y.Cao, G.Yu, C.Zhang, R.Menon and A.J.Heeger, Synth.Metals, 87,171 (1997)], the polypyrrole [J.Gao that mixes with DBSA (" DBSA "), A.J.Heeger, J.Y.Lee and C.Y.Kim, Synth.Metals 82,221 (1996)] or the like.
Also can adopt thin semi-transparent metals (as Au, Ag, Al etc.) layer as the electrode among the electrode among Fig. 1 11 and Fig. 2 13.The common thickness of this semi-transparent metals electrode is 50-500 , and optical transmittance is between 80% and 10%.Adopt suitable dielectric coated (often being the form that adopts multilayer dielectric heap) can strengthen transparency in interested spectral regions [such as, see S.M.Sze, Physics of Semiconductor Devices (John Wiley﹠amp; Sons, NewYork, 1981), Chapter 13].
The manufacturing materials of " back of the body " electrode 13 among Fig. 1 (and 11 among Fig. 2) is metal normally, as Ca, and Sm, Y, Mg, Al, In, Cu, Au or the like.Also can adopt metal alloy as electrode material.The making of this metal electrode can utilize, such as, thermal evaporation, electron beam evaporation, sputter, chemical vapour deposition (CVD), melting process or other technologies.The thickness of the electrode 13 among Fig. 1 (with 11 among Fig. 2) is not crucial, can be thicker after from hundreds of dusts to hundreds of micron.Can control so that obtain needed surface conductivity this thickness.
As needs, such as, the positive and negative both sides of photodiode all have measuring ability, and then above-mentioned transparent and trnaslucent materials also can be used as " back of the body " electrode 13 (with 11 among Fig. 2) among Fig. 1.
Row-column electrode shown in Fig. 3 and Fig. 4 can utilize graphically that known standard graphics technology realizes that these technology comprise shadow mask, photoetching, silk screen printing or punching press (microcontact printing) or the like in the semi-conductor industry.These methods are well-known for the personage who understands Display Technique.
The colour filter coating
What be concerned about in some applications is that polychrome detects or select the look detection.These can be by reaching optical sensor with suitable selective light active layer material when the colour filter coating is connected.
A kind of application is the optical sensor with selected spectral response, is 500 to 600nm such as spectral region.A kind of effective method is to take the organic photoelectric diode (such as the photodiode that adopts MEH-PPV) that has in the low-yield cut-off wavelength of 600nm, and the logical filter (cut-off wavelength is 500nm) of long wave wavestrip is placed the front.The spectral response of semiconductor oligomer and polymer can be controlled by changing side chain or backbone structure.Such as, light slit can be transferred to 700nm from 500nm by the side chain that changes the PPV system.The method that another select tape is logical is to place bandpass optical filter in the front of the organic photoelectric diode with wide spectral response.
It is often interesting in light image is used to panchromatic detection.This can reach by sensor element (pixel) is divided into three sub-pixels, these three sub-pixels are respectively to red (600-700nm), green (500-600nm) and blue (400-500nm) spectral regions respond, with common similar that look uses in the LCD color display technology.
A kind of simply and effectively summary of the scheme of full-colour image transducer is shown in Fig. 4.In this scheme, photodiode array is by constituting without patterned monolithic active layer.The active region is determined by row-column electrode.The spectral response of these organic photoelectric diodes should cover whole visible region (400-700nm).The colored selection is by placing the color filter plate realization in transparency electrode the place ahead.Have multiple organic material or mixture and have the photoresponse that can cover whole visible light district.Example has the PT derivative, as " P3OT ", poly (3-(4-octylphenyl) thiophene) [M.R.Anderson, D.Selese, H.Jarvinen, T.Hiertberg, O.Inganas, O.Wennerstrom and J.E.Osterholm, macromolecules 27,6503 (1994)], PTV and derivative thereof or the like.
Develop and be widely used in several chromatic filter technology that has in the color monitor that liquid crystal technology makes, comprised dye method, suspension pigment method, print process and electro-deposition method [M.Tani, Sugiura, Digest of SID 94 (Orlando, Florida)].Another kind of scheme is the multilayer dielectric matter coating of utilizing based on principle of optical interference.Because stability is better, so the pigment suspension method is an employed main method in the large-scale production.Having the design configuration (often being to adopt triangle, horizontal stripe shape or diagonal form zyklopisch) and the color filter plate of transparent electrode coating is the product of prior art and is the commercial goods of display industry.This substrate can be used for the making of full-colour image transducer shown in Figure 4.
Photodiode provided by the present invention except photon, also can be used to various ionizing particles itself are responded.The realization of this point is can the scintillation material that photon is sent in response take place to ionizing particle by add one in optical detector structure.This material can mix with active layer, can be used as independent stratum and exists, also can be used as substrate or transparency electrode a part and exist.In one example, this scintillation material is a fluorophor, exists as fluorescence coating.
The ionizing particle that utilizes the device of this structure to detect has high-energy photon, electronics, X ray, characteristic X-ray (characteristics of X-ray), β particle and sign gamma rays.The radiation of the specific wavelength in deep ultraviolet and X ray spectral regions also can utilize this organic photoelectric diode directly to detect.These wavelength are corresponding with the bottom of idle molecular orbit (LUMO) minimum from interior nuclear energy level (can be with) optical transition to energy or conduction band.
The infrared region radiation that photon energy is lower than the optical absorption band of light active material can be adopted similar mode by fluorescence coating the low energy infrared photon to be converted to the high energy light photon and detect.
Voltage of the present invention switches the organic photoelectric diode provides the basis of a kind of manufacturing based on the low-cost 2D imageing sensor of large scale of x-y addressable passive diode array.This photodiode demonstrates very high luminous sensitivity (normally at 30-300mA/W) under given bias voltage, and is actually zero response at bias voltage near interior demonstrating during at current potential.Like this, the one-row pixels in the ranks matrix of this photodiode can make this row chosen near interior at current potential by other bias voltages of going by selected row is arranged to reverse bias.When adopting this mode, can eliminate crosstalking between the pixel of different rows.Image information in the pixel in the select row still all can correctly be read under paralleling model at series model.Information in the pixel in other row can sequentially or by required row is arranged to reverse bias be read.X-y addressable organic photoelectric diode matrix can provide a kind of novel 2D imageing sensor, this transducer can create large-size device, low cost of manufacture, can on the substrate of needed shape or softness, make, and can create and other the optics or the hybrid device of electronic device.
For the linear diode array, the anode of diode (or negative electrode) can be used as common electrode and connects.Traditional saying is " anode altogether " or " common cathode ".
For anode altogether, this common anode links to each other with fixed voltage (lying prostrate such as zero) in the reading circuit.The negative electrode of each diode voltage Von (as+10V) or Voff as-0.2V or 0V) be connected with reading circuit.When the bias voltage of negative electrode was positive voltage (than the high current potential of the anode potential of this diode), this diode was in reverse bias condition.
In the occasion of common cathode, the fixed voltage in this common cathode and the reading circuit (such as zero volt) links to each other.The anode of each diode voltage Von (as-10V) or Voff (as+0.2V or 0V) be connected with reading circuit.When the bias voltage of anode was negative voltage (than the low current potential of the cathode potential of same diode), this diode was in reverse bias condition.
Reading circuit often is connected to become common anode mode with fixed potential (such as zero potential).
For the occasion of 2D matrix, when the row electrode was subjected to scanning, column electrode was connected (such as 0V) with fixed voltage.Selected row are applied the Von bias voltage, and the chosen bias voltage Voff that applies of other row.Reading circuit is positioned on the column electrode (based on such as the 0V current potential).When being in this type of drive, there are not electrode and drive circuit to disconnect (promptly not having electrode to float).The voltage that each diode on the select column (synchronization has only a column selection fixed, so in the mixing that does not have on the reading circuit from the picture signal of different pixels) bears is Von, and the voltage on the not selected diode is Voff.The anode electrode of each diode can or be connected with column electrode or with the row electrode.
Compare the present invention with corresponding techniques and have following advantage:
(i) luminous sensitivity of organic optical sensor is changeable.High luminous sensitivity can be connected (being generally 30-300mA/W) under selected reverse bias.When the external bias voltage of diode luminous sensitivity near with the inner potential correspondent voltage time can disconnect effectively.
(ii) can utilize organic photoelectric diode to make 2D, the passive imageing sensor of x-y addressable with switchable luminous sensitivity.Adopting this passive imageing sensor can obtain not have the data of crosstalking by suitable electronic impulse sequence reads.
(iii) can obtain polychrome detection and full-colour image sensing on the color filter plate by image array being connected with color filter plate or directly image sensor matrix being produced on.
(iv) the organic photoelectric diode array with by organic material, as solvable conjugated polymer, other advantages of the device of making (are easy to make large tracts of land and make needed shape on rigidity or soft substrates, can at room temperature process, be easy to optics, electrooptics, photoelectricity or electric device in conjunction with making hybrid device) combining to provide the 2D imageing sensor of the low-cost high pixel density of large scale for office automation, the production automation, biomedical articles and consumer electronics device use.
Example 1
Voltage switches light electric diode is to make by the calcium contact (13) of evaporating one deck 5000 on the front of MEH-PPV film 12, and film 12 wherein utilizes the rotary casting method to be coated on the ITO/ glass substrate 14 from solution.The part of glass substrate is coated with the contact layer 11 of tin indium oxide (ITO) in advance.The active region of each device is 0.1cm 2The MEH-PPV film is at room temperature to pour into a mould from the xylene solution of 0.5% (10mg/2ml) to form.The details synthetic about MEH-PPV can find [F.Wudl in the literature, P.-M.Allemand, G.Srdanov, Z.Ni and D.McBranch, in Materials for Nonlinear Optics:Chemical Prospectives, edited by S.R.Marder, J.E.Sohn and G.D.Stucky (The American Chemical Society, Washington DC, 1991), p.683.].The thickness of active layer can be by changing the concentration of solution, and the rotary speed that changes swivel head is regulated with the way that applies a plurality of coatings.
The electricity data utilize Keithley 236 source determination units to obtain.Excitaton source is a tungsten halogen lamp, filters (centre wavelength 430nm, bandwidth 100nm) through bandpass optical filter, and through collimating to form the surround of uniform 5mm * 10mm.Adopt one group of neutral filter to come the measured intensity relation.
Fig. 6 illustrates and utilizes the 430nm wavelength at 20mW/cm 2Illumination under the functional relation of photoelectric current (absolute value) and bias voltage.Photoelectric current under the 1.5V bias voltage is～3 * 10 -8A/cm 2, corresponding to luminous sensitivity be 45mA/W and quantum efficiency be 13%el/ph-be increased to 9 * 10 under the reverse bias of 10V -4A/cm 2The ratio position 3 * 10 of the luminous sensitivity between two kinds of bias voltages -4, like this, luminous sensitivity is actually zero under the 1.5V bias voltage.Big like this difference makes it possible to achieve the A/D converter that resolution is 8-12 bit (position).
From NW/cm 2To tens of mW/cm 2Whole measuring range in photoresponse almost linearly along with luminous intensity (I 0.92-1) increase.At 20mW/cm 2Do not observe saturated sign under (maximum light intensity in this measures).
Other metals, as Al, In, Cu, Ag etc. as counterelectrode 13 (see figure 1)s, are negative electrodes in these devices also.In all these devices, all observe the luminous sensitivity among the similar Fig. 5 of being shown in.The open circuit voltage of the inner potential of payment photodiode changes with the work function of metal; Open circuit voltage is determined by the work function difference between metallic cathode and the ito anode.Table 1 has been listed adopting the resulting open circuit voltage of MEH-PPV photodiode of several metal electrodes.
This example demonstrates high luminous sensitivity and can utilize the MEH-PPV organic photoelectric diode that is under the reverse bias to obtain.Under given reverse bias, can obtain desired luminous sensitivity.This luminous sensitivity can be switched under suitable bias voltage, and this bias voltage depends on selected electrode material.As shown in table 1, have metal that work function is higher than 4V and can be used as electrode in the organic photoelectric diode air-stable.This example also demonstrates the wide dynamic range of organic photoelectric diode, and this dynamic range is enough to make image detection to use multi-grey level.
Table 1: the open circuit voltage in ITO/MEH-PPV/ metal photodiode
Metallic cathode Ca Sm Yb Al In Ag Cu
V off(V) 1.5 1.5 1.5 1.1 0.9 0.7 0.4
Example 2
With the element manufacturing in the example 1 on the ITO/PET of softness substrate.The thickness that is used as the PET sheet of substrate is 5-7 Mill (150-200mm).Can be observed similar device performance.
This example demonstrates voltage switches light electric diode and can make and become the thin type structure, flexible form, or make and become desired shape to satisfy the specific (special) requirements in concrete the application.
Example 3
With the element manufacturing in the example 1 on glass and PET substrate.In these devices, ito anode 11 is by the organic conductive coating or adopt the ITO of conduction organic film covering to replace.PANI-CSA and PEDT/PSS are as machine electrode is arranged.Between the utilization of PANI-CSA layer-cresol liquor forms [the preparation details of PANI solution and PANI-CSA film is disclosed in U.S. Patent No. 5,232,631 in] through rotary casting.The PEDT/PSS film is water slurry [the Bayer Evaluation product by the Bayer supply, TP AI 4071] (1.3%W/W) cast form, can find [G.Heywang and F.Jonas, Adv.Materials 4,116 (1992)] in the literature about its synthetic details.Afterwards the film of being poured into a mould is toasted a few hours at vacuum oven or in the N2 drying box at 50-85 ℃.In the occasion of PEDT/PSS, at last film is being higher than under 100 ℃ the temperature baking several minutes to finish this dry run.The THICKNESS CONTROL of conductive polymer electrodes arrives between thousands of dusts at hundreds of dusts.
The optical transmission spectrum of polymeric anode electrode shown in Figure 7 comprises the data of PANI-CSA and PEDT-PSS.Normal eye's spectral response V (λ) also is shown among Fig. 7.Data show that these organic conductive electrodes can be applicable to use the optical sensor in the visible range.In addition, the PEDT-PSS electrode also is applied to ultraviolet (250-400nm) and near infrared region.Like this, polymer electrode just can be applicable to panchromatic (white or R, G, B three looks) detects.
Except the electrode that adopts independent PANI-CSA and PEDT-PSS to make, the two-layer electrode that device also adopts ITO/PANI-CSA and ITO/PEDT-PSS to make.In these occasions, polymer electrode is cast on the thin layer (thickness is hundreds of angstrom units) so that the optical transmittance maximum.Organic luminescent device with two-layer electrode demonstrates device performance, injects and device stability as charge carrier) improvement arranged.Its example is shown in U.S. Patent application No.08/205, and 519 and No.08/609,113.
Have organic anode electrode or two-layer electrode device luminous sensitivity be shown in similar among Fig. 6; Promptly in reverse bias be-5V is tens of mA/W to about-10V scope.
This example demonstrates can utilize the electrode material of conducting polymer materials as photodiode and imageing sensor.These plasticity electrode materials can provide the electrode chance of making soft or collapsible form.This example also demonstrates polymer electrode and can be inserted between metal-oxide transparent electrode (as tin indium oxide (ITO)) and the active layer to change interfacial property and device performance.
Example 4
Repeat the device of example 1.A resilient coating is inserted between ITO and the MEH-PPV layer to reduce the leakage current by the pin hole shortcoming in the active layer.Make that the material of resilient coating is spendable PAZ, TPD (by the chemical vapour deposition technique preparation) and a PVK (from the cyclohexanone solution casting).The thickness of resilient coating is 100-500 .The photoresponse of these devices and shown in Figure 6 similar.Yet in these devices, the value of dark current (micro-short circuit owing to the pin hole in the active layer causes sometimes) can reduce.In the device of these no short circuits, under DC operation, can detect little to 10nW/cm 2Photon stream.In these devices, open circuit voltage is 1.6～1.7V, the device in a little higher than example 1.
This example demonstrates resilient coating can be inserted into the short circuit and the response of improvement device to the low light level to reduce device between active layer and the contact electrode.This resilient coating can be made or be made by polymeric material by the wet method casting process by chemical vapour deposition (CVD) or by organic molecule.
Example 5
Repeat the device of example 1.Active material MEH-PPV and anionic surfactant Li-CO436 are with mole ratios 0,1, and 5,10 and 20% mixes.Li-CO436 is by the Alipal CO436 (ammonium salt nonylphenoxy ether sulfate) synthetic [Y.Cao, U.S. Patent application No.08/888,316] of displacement reaction utilization by Phone Poulenc Co. supply.Al is as negative electrode.The Li-CO436 that luminous sensitivity utilization in the device mixes strengthens.Such as, the photoelectric current in the device of being made by MEH-PPV:Li-OC436 (10wt%) of comparing with the similar device that adopts Li-OC436 to make doubles.In addition, open-circuit condition voltage is transferred to 1.5V in ITO/MEH-PPV:Li-OC436 (20%)/Al device by the 1.1V in ITO/MEH-PPV/Al device (seeing example 1).In device, also can be observed similar effects with ITO/MEH-PPV/Li-OC436/Al structure.
This example demonstrates organic additive can add in the active layer or be inserted between active layer and the contact electrode to change device performance, comprises luminous sensitivity and open circuit voltage.
Example 6
Voltage switches light electric diode is to utilize with similar ITO/MEH-PPV:PCMB/ metal structure shown in Figure 1 to make.PCMB (a kind of C 60Derivative) as the acceptor of D-A centering, and MEH-PPV is as donor.The active region of these devices is～0.1cm 2Mixed solution is to be 2: 1 PCMB/ xylene solution by the weight ratio with 0.8% MEH-PPV and 2%.This solution is limpid, evenly, and can at room temperature handle.Solution is stored in N 2In the case more than 1.5 years and do not observe and assemble or be separated.Active layer be 1000-2000rpm (rev/min) rotating speed under form by solution rotating cast.Typical film thickness is 1000～2000 .Ca, Al, Ag, Cu and Au are with doing electrode 13.In each occasion, film all is to reach thickness 1000-5000  by vacuum evaporation deposition.
Fig. 8 illustrates the ITO/MEH-PPV:PCBCR/Al device and reaches I-V characteristic curve under the optical illumination in the dark.The thickness of mixture film is～2000 .Dark current when 3V at～1nA/cm 2Saturated, afterwards at high bias voltage (＞E g/ increase in the superlinearity mode under e).The reason of this effect can be summed up as Zener tunneling.Photoelectric current is measured.Photoelectric current under 0.65V is～1 * 10 -7A/cm 2, and under-10V bias voltage, rise to 5 * 10 -4A/cm 2Make-to-break ratio is～5000.Have luminous sensitivity and higher make-to-break ratio that thinner mixture film device demonstrates enhancing.Similarly luminous sensitivity is adopting other metals also to can be observed as in the device that electrode is made.These metals comprise Ag, Cu, Ca, Sm and Pb.
Use other organic molecules as light receptor, comprised C 60Utilize C 60Derivative, PCBM has prepared other mixtures.Utilization is by 1, and the MEH-PPV:PCMB of 2-dichlorobenzene (1, the 2-dichlorobenzene) solution processing has observed higher luminous sensitivity.Can reach 0.2A/W in this luminous sensitivity of 430nm wavelength place at bias voltage during for-2V.
This example demonstrates and can pass through with donor polymer and molecular receptor, as C 60, mix and further improve luminous sensitivity.At low relatively bias voltage and low electric field (～10 5V/cm) can obtain high luminous sensitivity down.This example also demonstrate the bias voltage that on device, applies offset its inner current potential of setting up (for the Al negative electrode for～0.65V) time, luminous sensitivity switches near zero.Data in this example show, because the level of dark current is very low, it is low to tens of nW/cm that the polymer photodiode can be used for detected intensity 2The low light level.Like this, the dynamic range of polymer photodiode can cover 6 more than the order of magnitude, from nW/cm 2To 100mW/cm 2
Example 7
Adopt 4.5cm * 4cm (18cm 2) and 3.8cm * 6.4cm (24.3cm 2) glass/ITO and PET/ITO substrate and utilize with example 6 in the similar course of processing made with example 6 in the similar device of device.Observe and be similar to I-V characteristic curve shown in Figure 8.Adopt the photodiode circumflexion of soft PET substrate making and do not change its luminous sensitivity.
This example demonstrates highly sensitive voltage switches light electric diode and can make and become large-sized device.Adopt soft substrate, optical sensor is flexible to be become desirable shape and is used for optics, physics and biomedical sector.
Example 8
Repeat to make and have employing by MEH-PPV:CN-PPV, a kind of by two kinds of high polymer mixtures that constitute as donor and acceptor polymer mutually, the active layer made from example 6 in the similar device of device.Ca and ITO are used separately as negative electrode and anode electrode.Observe with Fig. 8 in similar I-V characteristic curve, simultaneously open circuit voltage with according to the change in donor and the acceptor potential barrier between mutually desired identical mobile～1.2V.
Example 9
Repeat to make and have employing by own thiophene (6T): PCBCR, a kind of by two organic molecular species as donor and acceptor mixture mutually, the active layer made from example 6 in the similar device of device.
Example 8 demonstrates with example 9, and except the mixture shown in the example 6, the active layer of voltage switches light electric diode can also be the mixture of organic molecule, or the mixture of conjugated polymer.Data in these examples, the data with example 1 also demonstrate, and for given negative electrode, as Ca, open circuit voltage changes with the electronic structure of active material.
Example 10
Voltage switches the making employing P3OT of organic photoelectric diode as the active layer in the ITO/P3OT/Au structure.Reach the I-V characteristic curve under the optical illumination shown in Fig. 9 in the dark.Because the work function of Au is higher than ITO, the Au electrode is as the anode in these devices.Positive bias is defined as and applies a high potential on the Au electrode.Light is from the incident of negative electrode (ITO) electrode.In this experiment, adopted wavelength be the He-Ne laser of 633nm as light source, photon density is 10mW/cm 2
Interior in this photodiode is reduced near zero at current potential.Like this, the open-circuit condition of photodiode moves near zero volt.Photoelectric current is 1mA/cm when-12V 2, than high by 10 when the zero-bias 4Doubly.Similarly realizing I in the device Ph(-12V)/I Ph(0) rate value surpasses 1.5 * 10 5In the 633nm luminous sensitivity be～100mA/W, corresponding to the quantum efficiency of～20%ph/el.Dark current is lower than 5 * 10 in trial stretch -7A/cm 2Wide bias voltage scope (4～-12V) in photoelectric current/dark current ratio greater than 1000.
The open-circuit condition that this example demonstrates photodiode can change by suitable selection active material and electrode material.This voltage can be set near zero volt.The photodiode array that adopts this kind photodiode to make can utilize the unipolar pulse string to drive, thus but simplified driving circuit.Big break-make is switched when big photoelectric current/dark current ratio permission photodiode and be can be applicable to make the x-y addressable passive matrix with high pixel density and degree gray scale.
Example 11
Made a kind of 2D photodiode array with 7 row, 40 row.Pixel Dimensions is 0.7mm * 0.7mm.Space between column electrode and the row electrode is 1.27mm (0.05 ").The gross activity district is～2 " * 0.35 ".The typical I-V characteristic curve of pixel is shown in Figure 10.The white light that fluorescent lamp on the ceiling of laboratory sends is as light source, and intensity is～tens of μ W/cm 2This a little less than than employed light intensity in file scanner many.
The photodiode array that this example demonstrates pixelation can be made and become no short circuit and nothing is crosstalked.This example also demonstrates this device and can be applicable to luminous intensity and be equal to or less than microwatt/cm 2Occasion.Like this, to be used for image applications under the condition of the relative low light level be practicable to the polymer photodiode array.
Example 12
Developed a kind of sweeping scheme (seeing Figure 11) that is used for this photodiode array.Because the substantial connection of luminous sensitivity and voltage, the pixel column in the 2D photodiode array are optionally, and can utilize suitable bias voltage connection and make the pixel of adjacent lines remain incident light insensitive.Under this operational mode, the 2D matrix of the capable N of M physically row just turns to the linear diode array of the M element of N isolation approximately, and it respectively is listed as does not alternately crosstalk.This makes us remembering and is utilizing dimensional reduction to solve employed notion in the 2D integration, ∫ f (x, y) dxdy=∫ g (x) dx ∫ h (y) dy
Adopt the pulse train that the passive photodiode array of this 2D can scan the piece image utilization each row of this matrix to read.
Figure 11 illustrates instantaneous " snapshot " of the voltage distribution of doing in 7 * 40 photodiode arrays.Make a certain moment t, all pixels all add bias voltage+0.7V, have only the pixel exception in the row 1.Pixel in the row 1 all is added with bias voltage-10V, so that obtain high luminous sensitivity (thousands of mA/Watt).Information on some pixels in the row 1 both can also can be read by (with the N channel simulation switch) sequence of connecting by (with N channel switcher and A/D converter) in parallel.Pixel in other row can be by switching to the row bias voltage+10V and being selected successively from 0.7V.Column selection can be used digital shift register.
For simplified driving circuit, preferably optical sensor can 0V and reverse bias (2 to-switch between 10V).This kind adopts the unipolarity voltage switches light electric diode of ITO/P3OT/Au to be shown in the example 10.
Example 13
Once select a width of cloth multi-grey level image, and utilized 7 * 40 photodiode arrays to scan according to the sweeping scheme of in example 12, being discussed image.Original image and the image of reading photographic process record.The image of reading is with splendid fidelity replicating original image.
This example demonstrates the pixel element that voltage switches light electric diode can be used as ranks matrix as shown in Figure 3.Photodiode on each pixel can be from row and column electrode addressing effectively.The image information of multi-grey level can be read and be undistorted.
Example 14
Made with example 10 similar devices and measured spectral response at reverse bias device during for-15V.Data are shown in Figure 12.With significantly decline is different in short wavelength region medium sensitivity in common inorganic photodiode, the P3OT photodiode demonstrates straight relatively response to the wavelength that is shorter than 630nm; When being lower than 350nm the obvious decline of sensitivity be since have the ITO coating glass substrate transmissivity by the institute cause.For the bias voltage of-15V, (quantum yield～80%el/ph) is with to utilize ultraviolet to strengthen the numerical value that the Si diode obtains identical can to reach 0.35A/W in the sensitivity of 540nm place.Similarly luminous sensitivity continues up to the ultra-violet (UV) band less than 400nm.
The response that this example demonstrates the anode photodiode of high luminous sensitivity can cover ultraviolet and whole visible light district simultaneously.
Example 15
Made of the response of a kind of voltage switches light electric diode with the eye response V (λ) that obtains similar human eye.The making of this device is by applying long wavelength's bandpass optical filter on the front surface of the glass substrate of device, is similar to the sort of shown in Figure 15.Coating material in this example is the PPV layer, is to be converted by its matrix polymer film under 230 ℃.Adopt and do not adopt the device luminous sensitivity of this this filter to be shown in Figure 13 (a).The transmissivity that lists file names with the eye response V (λ) (seeing Figure 13 (b)) of human eye and PPV filter as a comparison.The photoresponse of P3OT diode overlaps with V (λ) when wavelength is longer than 560nm, and the optical transmittance of PPV filter is consistent with V (λ) to the wide district of 550nm at 450nm.
This example demonstrates consistent polymer photodiode with the eye response V (λ) that is equivalent to human eye basically, and this for optical engineering and biophysics/biomedical applications highly significant.
Example 16
Utilize MEH-PPV:C 60Poly-mixture has been made a day blind UV-detector.Use ITO and Al as anode and cathode material.Device is to make at the ultraviolet bandpass optical filter of buying from Melles Griot Inc. (production number No.03 FCG 177).Figure 14 is illustrated in-the 2V spectral response of the UV-detector of operation down.For relatively with the MEH-PPV on the ITO/ glass substrate: C60The spectral response of photodiode is drawn with the response that ultraviolet strengthens the Si photodiode.Data show that the polymer UV-detector is to the ultra-violet radiation sensitivity of 300-400nm, and luminous sensitivity is～150mA/W that the luminous sensitivity that strengthens the Si photodiode with ultraviolet is comparable.Data show that also the luminous sensitivity of MEH-PPV photodiode is subjected to the inhibition of optical bandpass filter and (surpasses 10 3Doubly).
This example demonstrates by voltage being switched the integrated blind UV-detector of highly sensitive day of producing of the logical filter of organic photoelectric diode and ultra high-frequency band.
Example 17
Repeat example 14, except active layer is the PTV thin layer.The spectral response of PTY photodiode is shown in Figure 15 (a), and this response has covered from 300 to 700nm spectral regions; It is whole visible light district.Can select the look detection by insert bandpass optical filter or long wave filter in detector the place ahead.Figure 15 (b) illustrates the blue pixel of utilizing color filter plate and PTV photodiode array to make, the response of green pixel and red pixel.Corresponding R, G, the transmissivity of B chromatic filter is shown in Figure 15 (c).
This example demonstrates by the polymeric image transducer is combined with color filter plate, can utilize the polymer photodiode array with the whole visible light of covering to reach R, G, the colored identification of B.
Example 18
Can carry out RGB (R, G, B) the colored detection according to the scheme of Fig. 5.The material that is used for making active layer is the PPV that has in the long wavelength cutoff of 500nm; Poly (dihexyloxyphenylene vinylene), " PDHPV " has the long wavelength cutoff at 600nm; And has a PTV in the long wavelength cutoff of 700nm.Film is that the form with its matrix polymer is formed by solution casting, and thickness is 1000 -3000 .Transformation to conjugate form is to carry out under 150-230 ℃ temperature.The conjugated thin film of Xing Chenging is insoluble to organic solution by this way.Like this, these materials on single substrate are patterned into and are point or the banded lithographic printing that can utilize standard, silk screen printing or the like method.The normalization photoresponse of these photodiodes is shown in Figure 16 (a).Used the ITO/ glass substrate in this test, this substrate is to visible transparent, and opaque to ultraviolet light.
Red and green choice look detects and can realize (this operation utilizes reading circuit to be easy to carry out) by the signal from these photodiodes being carried out differential.The rate response of these photodiodes is shown in Figure 16 (b).Red detection (utilizing the response of 600-700nm) is to realize by cutting from the signal from the PDHPV photodiode from the signal of PTV photodiode.Green test (utilizing the response of 500-600nm) is to realize by cutting from the signal from PTV from the signal of PDHPV.Blue detection directly obtains from the PPV photodiode.
This example demonstrates R, and G, B select look to detect and the full-colour image transducer can graphically be realized by make three kinds of photosensitive materials on the substrate with uniform optical characteristic.
Example 19
Voltage switches light electric diode utilizes conjugated polymer poly (p-phenyl vinylene), and PTV makes as light active material.The PPV film show utilize the rotary casting method after non-conjugated matrix polymer solution is coated on the ITO substrate by changing conjugate form in 3 hours into 200-230 ℃ of heating.Al is as back electrode.The active region is～0.15cm 2This photodiode shown in Figure 17 reaches the I-V characteristic curve under the optical illumination in the dark.Photoelectric current/dark current ratio logarithm mW/cm 2White-light illuminating be about 10 -4Such as, with comparing of photodiode in the example 1, observed herein dark current is low relatively under the situation of forward bias.This detects with regard to allowing to carry out light under two kinds of bias voltages of Direct/Reverse, as shown in figure 17.Luminous sensitivity can be switched to on-off by changing outer bias voltage.Such as, under white light (or ultraviolet light) illumination ,+5V or-5V under 2000 times of photoelectric currents to photoelectric current at+0.95V (or 0.3V).
This example demonstrates photodiode can connect (exceed with the corresponding voltage of open-circuit condition near) by applying forward bias or reverse bias.Can to work under two kinds of switch polarity be useful to photodiode in some circuit design and in using.
Example 20
The voltage switches light electric diode of making has heterojunction as its active layer.They have ITO/ donor layer/receptive layers/metal structure.The employed material of donor layer is MEH-PPV and PPV.The employed material of receptive layers is to utilize physical vapour deposition (PVD) to pile up the C that forms 60And utilize cast or rotary casting to pile up PCBM and the PCBCR that forms.Shown in Figure 18 MEH-PPV/C 60The data that photodiode is set.
In these devices, observe many knots (multiple junctions).See the inherent current potential (forward bias is as the positive bias that is applied on the ITO) of one～0.5V in the I-V characteristic curve that records in the dark.When being thrown light on, device finds another knot.Total effectively potential barrier is～0,15V (reindexing).Photoelectric current/dark current ratio is 10 in very wide bias voltage scope 4Voltage switches luminous sensitivity all can be seen under positive and negative two kinds of bias voltages.Such as ,+2V and+the 0.15V bias voltage under the on/off of photoelectric current than being～10 3
This example demonstrates photodiode can utilize the heterojunction form making that is had the organic semiconductor observation of different electronic structures by two kinds (or more).This photosensitive pattern can obtain under positive and negative two kinds of bias voltages in this device.

Claims (19)

1. a switchable organic photoelectric diode detector comprises photodiode and voltage source, and described photodiode has inherent current potential and comprises:
Support substrates;
Be disposed at first electrode on the described support substrates;
Be disposed at the photolytic activity organic layer on described first electrode;
Be disposed at second electrode on the described photolytic activity organic layer; And
Be used on described first electrode and described second electrode, optionally applying the described voltage source of switched voltage, described switched voltage is in the luminous sensitivity that produces under reverse or the forward bias more than the 1mA/W, and is substantially equal to produce near zero luminous sensitivity under the situation in the cut-off bias of current potential in described at numerical value.
2. photodiode detector as claimed in claim 1, wherein moving bias voltage is the operation reverse biased.
3. photodiode detector as claimed in claim 1, wherein moving bias voltage is the operation forward bias.
4. reading circuit that utilizes the photodiode detector of claim 1, wherein move bias voltage greater than 1V and represent the on-state of photodiode, described detector has luminous sensitivity greater than 1mA/W in described on-state, and wherein the cut-off bias representative at the off state of the photodiode of the null luminous sensitivity of reading circuit output.
5. photodiode array, its formation comprises the photodiode detector of a plurality of claims 1, described detector has the photodiode that is arranged in array, and each in the described photodiode can be carried out selectable addressing as the pixel of described array.
6. photodiode array as claimed in claim 5, wherein said array is a linear array, have common anode and independent negative electrode, described anode altogether is connected with the fixed anode magnitude of voltage, and independent negative electrode is connected with switched voltage, and this voltage can be greater than anode voltage and can produce the voltage of luminous sensitivity and not produce between second voltage of luminous sensitivity and change.
7. photodiode array as claimed in claim 5, wherein said array is a linear array, have common cathode and independent anode, described common cathode is connected with the fixed negative pole magnitude of voltage, and independent anode is connected with switched voltage, and this voltage can be less than cathode voltage and can produce the voltage of luminous sensitivity and not produce between second voltage of luminous sensitivity and change.
8. photodiode array as claimed in claim 5, wherein said array comprises delegation's photodiode and at least one row photodiode at least, each row anode together connects, each row is connected with common cathode, first electrode of each photodiode of row is connected with described anode altogether, second electrode of each photodiode of row is connected with described common cathode, and described voltage source is used for described switched voltage is put at least one common anode and at least one common cathode so that activate at least one pixel of described array selectively.
9. photodiode array as claimed in claim 8, wherein said switched voltage are to put on a plurality of altogether anodes and at least one common cathode so that activate at least one row pixel of described array selectively.
10. photodiode array as claimed in claim 8, wherein said switched voltage are to put on a plurality of common cathodes and at least one common anode so that activate the one-row pixels at least of described array selectively.
11. photodiode array as claimed in claim 9, wherein the row with selected activation call over, and described selectivity is read and comprised:
Selected row of order exciting light electric diode as described below, that is,
The operation bias voltage is put on the common cathode that links to each other with described selected row and all common anodes, and described working voltage makes the luminous sensitivity of each photodiode generation of selected row greater than 1mA/W;
Cut-ff voltage is put on remaining negative electrode and all anodes, equal described inherent current potential on the described cut-ff voltage numerical value and on the photodiode of all row except that selected row, produce approaching zero luminous sensitivity; And
Call over the output of the select column generation of photodiode.
12. photodiode array as claimed in claim 9, wherein the row with selected activation calls over, and described selectivity is read and comprised:
A selected row of order exciting light electric diode as described below, that is,
The operation bias voltage is put on the common anode that links to each other with described selected row and all common cathodes, and described working voltage makes the luminous sensitivity of each photodiode generation of selected row greater than 1mA/W;
Cut-ff voltage is put on remaining anode and all negative electrodes, equal described inherent current potential on the described cut-ff voltage numerical value and on the photodiode of all row except that selected row, produce approaching zero luminous sensitivity; And
Call over the output of the select row generation of photodiode.
13. but the scanning array of a voltage switching organic photoelectric diode, each photodiode has inherent current potential and predetermined luminous sensitivity scope, and described array comprises:
Support substrates;
First electrode layer of forming by at least one lineation electrode that is disposed at along first direction on the described support substrates;
Be disposed at the photolytic activity organic layer on the described lineation electrode;
By be disposed at the second electrode lay that a plurality of lineation electrodes on the described photolytic activity organic layer are formed along second direction with described first direction crosscut; And
Be used at least one electrode of at least one electrode of described first electrode layer and described the second electrode lay, applying the described voltage source of switched voltage, thereby described switched voltage is in the luminous sensitivity that produces at least one selected photodiode under the operation bias voltage more than the 1mA/W, and is substantially equal to produce near zero luminous sensitivity under the situation in the cut-off bias of current potential in described at numerical value.
14. but as the scanning array of claim 13, wherein moving bias voltage is the operation reverse biased.
15. but as the scanning array of claim 13, wherein moving bias voltage is the operation forward bias.
16. photodiode array as claimed in claim 5, wherein said array is a two-dimensional array, has a plurality of common anode and a plurality of common cathodes on second direction on first direction.
17. photodiode array as claim 16, wherein read by applying a given magnitude of voltage from the signal of photodiode array, this magnitude of voltage can not produce luminous sensitivity at all common anodes with except being applied with bias voltage on it on all common cathodes the common cathode that will read that produces luminous sensitivity.
18. photodiode array as claim 17, wherein read by applying a given voltage from the signal of photodiode array, this given voltage can not produce luminous sensitivity at all common cathodes with except being applied with bias voltage on it on all common anodes the common anode that will read that produces luminous sensitivity.
19. as the photodiode array of claim 17 or 18, wherein the independent photodiode that is connected with the common electrode of reading is to read individually by apply bias voltage on the independent electrode that produces luminous sensitivity separately.
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Families Citing this family (55)

* Cited by examiner, † Cited by third party
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GB0002958D0 (en) * 2000-02-09 2000-03-29 Cambridge Display Tech Ltd Optoelectronic devices
EP1158775A1 (en) 2000-05-15 2001-11-28 EASTMAN KODAK COMPANY (a New Jersey corporation) Self-illuminating colour imaging device
JP4278080B2 (en) * 2000-09-27 2009-06-10 富士フイルム株式会社 High sensitivity light receiving element and image sensor
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US6670213B2 (en) 2001-10-10 2003-12-30 Cambridge Display Technology Limited Method of preparing photoresponsive devices, and devices made thereby
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DE10157945C2 (en) * 2001-11-27 2003-09-18 Osram Opto Semiconductors Gmbh Process for producing an organic, electroluminescent display and an organic, electroluminescent display
AU2003262413A1 (en) * 2002-04-16 2003-11-03 The Regent Of The University Of California High-performance and low-cost plastic solar cells
DE10244176A1 (en) 2002-09-23 2004-04-08 Siemens Ag X-ray detector for use in digital imaging, especially CT applications, has a multi-layer structure with interleaved support, fluorescing and photo-sensor layers to permit energy-resolved radiation detection
DE10244178A1 (en) 2002-09-23 2004-04-08 Siemens Ag X-ray detector used in computer tomography comprises a luminescent layer for producing electromagnetic radiation, an electrically conducting bottom electrode, a photodetector layer, and an electrically conducting top electrode
DE10255964A1 (en) 2002-11-29 2004-07-01 Siemens Ag Photovoltaic component and manufacturing process therefor
DE10330595A1 (en) 2003-07-07 2005-02-17 Siemens Ag X-ray detector and method for producing X-ray images with spectral resolution
JP2005032793A (en) * 2003-07-08 2005-02-03 Matsushita Electric Ind Co Ltd Organic photoelectric converter
DE10361713B4 (en) 2003-12-30 2008-02-07 Qimonda Ag Use of charge-transfer complexes of an electron donor and an electron acceptor as a basis for resistive storage and storage cell containing these complexes
KR101022688B1 (en) * 2004-03-22 2011-03-22 후지필름 가부시키가이샤 Photodetector
DE102004026618A1 (en) * 2004-06-01 2005-12-29 Siemens Ag X-ray detector
GB0413398D0 (en) 2004-06-16 2004-07-21 Koninkl Philips Electronics Nv Electronic device
AT500855B1 (en) * 2004-09-08 2006-04-15 Bioident Biometric Technologie DEVICE FOR EVALUATING BIOCHEMICAL SAMPLES
US20090134385A1 (en) * 2005-06-16 2009-05-28 Siemens Aktiengesellschaft Organic Line Detector and Method for the Production Thereof
DE102005037290A1 (en) * 2005-08-08 2007-02-22 Siemens Ag Flat panel detector
JP4872051B2 (en) * 2006-03-20 2012-02-08 パナソニック電工株式会社 Organic thin film solar cell
GB2443204A (en) 2006-10-04 2008-04-30 Sharp Kk Photosensor and ambient light sensor
KR20100016643A (en) * 2007-04-19 2010-02-12 바스프 에스이 Method for forming a pattern on a substrate and electronic device formed thereby
KR101328569B1 (en) 2012-01-10 2013-11-13 한국과학기술원 Hot Electron Based Nanodiode Sensor and Method for Preparing the Same
CA2887101A1 (en) * 2012-10-05 2014-04-10 University Of Southern California Energy sensitization of acceptors and donors in organic photovoltaics
EP2936052B1 (en) 2012-12-19 2021-04-28 Basf Se Detector for optically detecting at least one object
JP6440696B2 (en) 2013-06-13 2018-12-19 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ Detector for optically detecting the orientation of at least one object
KR102252336B1 (en) * 2013-06-13 2021-05-14 바스프 에스이 Optical detector and method for manufacturing the same
US9989623B2 (en) 2013-06-13 2018-06-05 Basf Se Detector for determining a longitudinal coordinate of an object via an intensity distribution of illuminated pixels
US9557856B2 (en) 2013-08-19 2017-01-31 Basf Se Optical detector
US9665182B2 (en) 2013-08-19 2017-05-30 Basf Se Detector for determining a position of at least one object
US9244356B1 (en) 2014-04-03 2016-01-26 Rolith, Inc. Transparent metal mesh and method of manufacture
WO2015183243A1 (en) 2014-05-27 2015-12-03 Rolith, Inc. Anti-counterfeiting features and methods of fabrication and detection
JP6660931B2 (en) 2014-07-08 2020-03-11 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ Detector for determining the position of at least one object
FR3025052B1 (en) 2014-08-19 2017-12-15 Isorg DEVICE FOR DETECTING ELECTROMAGNETIC RADIATION IN ORGANIC MATERIALS
KR102452393B1 (en) 2014-09-29 2022-10-11 바스프 에스이 Detector for optically determining a position of at least one object
US20160111473A1 (en) * 2014-10-17 2016-04-21 General Electric Company Organic photodiodes, organic x-ray detectors and x-ray systems
CN107003785B (en) 2014-12-09 2020-09-22 巴斯夫欧洲公司 Optical detector
US9786855B2 (en) 2014-12-30 2017-10-10 Indian Institute Of Technology Bombay Micro electro mechanical system (MEMS) based wide-band polymer photo-detector
KR102282218B1 (en) * 2015-01-30 2021-07-26 삼성전자주식회사 Imaging Optical System for 3D Image Acquisition Apparatus, and 3D Image Acquisition Apparatus Including the Imaging Optical system
WO2016120392A1 (en) 2015-01-30 2016-08-04 Trinamix Gmbh Detector for an optical detection of at least one object
WO2017012986A1 (en) 2015-07-17 2017-01-26 Trinamix Gmbh Detector for optically detecting at least one object
US10412283B2 (en) 2015-09-14 2019-09-10 Trinamix Gmbh Dual aperture 3D camera and method using differing aperture areas
EP3491675B1 (en) 2016-07-29 2022-11-16 trinamiX GmbH Optical sensor and detector for optical detection
EP3532864A1 (en) 2016-10-25 2019-09-04 trinamiX GmbH Detector for an optical detection of at least one object
KR102575104B1 (en) 2016-10-25 2023-09-07 트리나미엑스 게엠베하 Infrared optical detector with integrated filter
US10948567B2 (en) 2016-11-17 2021-03-16 Trinamix Gmbh Detector for optically detecting at least one object
US11860292B2 (en) 2016-11-17 2024-01-02 Trinamix Gmbh Detector and methods for authenticating at least one object
EP3565238B1 (en) * 2016-12-27 2023-07-19 Panasonic Intellectual Property Management Co., Ltd. Imaging device, camera and imaging method
CN110366780B (en) * 2017-01-15 2023-04-25 赛因托鲁株式会社 Photodetector array
US11060922B2 (en) 2017-04-20 2021-07-13 Trinamix Gmbh Optical detector
JP7237024B2 (en) 2017-06-26 2023-03-10 トリナミクス ゲゼルシャフト ミット ベシュレンクテル ハフツング a detector for determining the position of at least one object
KR102370763B1 (en) 2017-09-26 2022-03-04 삼성전자주식회사 An electronic device controlling a camera based on an external light and control method
TWI783805B (en) * 2021-12-01 2022-11-11 天光材料科技股份有限公司 Optoelectronic semiconductor structure

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5504323A (en) * 1993-12-07 1996-04-02 The Regents Of The University Of California Dual function conducting polymer diodes

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