US3858074A - Photoelectric transducer element including a heterojunction formed by a photoelectric transducer film and an intermediate film having a larger energy gap than the photoelectric transducer film - Google Patents

Photoelectric transducer element including a heterojunction formed by a photoelectric transducer film and an intermediate film having a larger energy gap than the photoelectric transducer film Download PDF

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Publication number
US3858074A
US3858074A US00304050A US30405072A US3858074A US 3858074 A US3858074 A US 3858074A US 00304050 A US00304050 A US 00304050A US 30405072 A US30405072 A US 30405072A US 3858074 A US3858074 A US 3858074A
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United States
Prior art keywords
photoelectric transducer
film
image pickup
pickup tube
transducer film
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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US00304050A
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English (en)
Inventor
M Fukai
S Fujiwara
H Serizawa
O Eguchi
Y Kuramoto
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Panasonic Holdings Corp
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Matsushita Electric Industrial Co Ltd
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Priority claimed from JP46089622A external-priority patent/JPS5037513B2/ja
Priority claimed from JP47003265A external-priority patent/JPS5120242B2/ja
Priority claimed from JP47096428A external-priority patent/JPS524404B2/ja
Application filed by Matsushita Electric Industrial Co Ltd filed Critical Matsushita Electric Industrial Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J29/00—Details of cathode-ray tubes or of electron-beam tubes of the types covered by group H01J31/00
    • H01J29/02—Electrodes; Screens; Mounting, supporting, spacing or insulating thereof
    • H01J29/10—Screens on or from which an image or pattern is formed, picked up, converted or stored
    • H01J29/36—Photoelectric screens; Charge-storage screens
    • H01J29/39—Charge-storage screens
    • H01J29/45—Charge-storage screens exhibiting internal electric effects caused by electromagnetic radiation, e.g. photoconductive screen, photodielectric screen, photovoltaic screen
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F30/00—Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors
    • H10F30/20—Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors the devices having potential barriers, e.g. phototransistors
    • H10F30/21—Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors the devices having potential barriers, e.g. phototransistors the devices being sensitive to infrared, visible or ultraviolet radiation
    • H10F30/22—Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors the devices having potential barriers, e.g. phototransistors the devices being sensitive to infrared, visible or ultraviolet radiation the devices having only one potential barrier, e.g. photodiodes
    • H10F30/222—Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors the devices having potential barriers, e.g. phototransistors the devices being sensitive to infrared, visible or ultraviolet radiation the devices having only one potential barrier, e.g. photodiodes the potential barrier being a PN heterojunction

Definitions

  • Abrikosov et a1. Semiconducting lI-Vl, lV-Vl &
  • ABSTRACT A photoelectric transducer element having high photo and spectral sensitivity in which a material with an energy band gap larger than that of a photoelectric transducer film is interposed between the photoelectric transducer film and a transparent conductive film.
  • the present invention relates to a photoelectric transducer element, or more in particular to a photoelectric transducer element suitably used as a target for an image pickup tube.
  • CdS, CdSe and mixed crystals thereof are well known as materials suitable for a photoelectric transducer ele' ment.
  • their high sensitivity however, they can not be used as a target of an image pickup tube due to considerable dark current accompanying them and their slow responsiveness to light.
  • their spectral sensitivity is low for wavelengths other than those corresponding to their energy band gaps, and materials with a spectral sensitivity curve which is flat over the entire range of visible light have yet to be developed.
  • Well-known conventional materials used as targets for image pickup tubes include a film of antimony trisulfide Sb S for vidicons, lead oxide PbO for PbO vidicons and a silicon photodiode array for silicon vidicons. All of these materials, however, have their problem points as mentioned below.
  • the vidicon has the sensitivity in the order of 200 to 300 ptA/lm and the dark current of 20 nA per one'inch vidicon, and is used as a camera for industrial television, but its low sensitivity limits the images capable of being picked up to those of brightness in the order of 5 1x or more.
  • Another disadvantage of the vidicon is a considerable amount of undesirable afterimage and lay-image accompanying the pickup operation, making it unsuitable for use with a color image pickup tube for television broadcasting.
  • PbO vidicon With a very small amount of dark current of 0.2 nA/l.5 inches and a little lay-image, this is widely used with an image pickup tube for television broadcasting. But its sensitivity is as low as 300 uA/lm which is a little higher than that of the vidicon but still inadequate. Since this has no spectral sensitivity for a red light with wavelength of 650 nm or more, the use of this PbO vidicon for the red color image pickup tube of the threetube type camera requires PbS to be added to PbO so as to increase its sensitivity to about 850 nm.
  • Si vidicon This image pickup tube has the advantages of a sensitivity 20 times that of the vidicon and the absence of undesirable after-image. But is characteristics associated with lag-images and resolution are inferior to those of the PhD vidicon, making it unsuitable for use with an image pickup tube for television broadcasting.
  • Another disadvantage of this tube lies in that the peripheral portions of an image of a very bright object are blurred thereby to undesirably enlarge the image to a size two or three times the original image.
  • the photoelectric transducer element according to the present invention is characterized in that a material with an energy band gap larger than that of a photoelectric transducer film is interposed between a transparent conductive film and the photoelectric transducer film.
  • FIG. 1 is a sectional view showing an embodiment of the present invention
  • FIG. 2 is a diagram comparing the spectral sensitivity of a photoelectric transducer element with a ZnSe film interposed between the transparent conductive film and the photoelectric transducer film with that of a photoelectric transducer element without any ZnSe film interposed;
  • FIG. 3 is a diagram showing the spectral sensitivity of ZnSe-Zn,,Cd,.,,Te;
  • FIG. 4 is a diagram showing the principle on which the responsiveness to light is measured
  • FIG. 5 is a graph showing how the dark current varies with the composition of ZnSe-(Zn,,Cd,. u )0.9s( 2 a)0.o.-s;
  • FIG. 6 is a diagram showing how the photoelectric current varies with the composition of the ZnSeu 1-u )o.95( z alopsi
  • FIG. 7 is a diagram showing the spectral sensitivity of the photoelectric transducer element consisting of Zny l-J/ )0.95( 2 3)0.05;
  • FIG. 8 is a characteristic diagram showing the spectral sensitivity of the photoelectric transducer element consisting of ZnSe-(Zn Cd Te),(ln Te and
  • FIG. 9 is a characteristic diagram showing the spectral sensitivity of the photoelectric transducer element Consisting Of ZIIS SC AZn CCl T) I11 Tc
  • a transparent conductive film 2 of, say, In O or SnO is formed on a glass substrate 1
  • a photoelectric transducer film 4 is formed on the transparent conductive film 2 with an intermediate film 3 therebetween having an energy band gap larger than that of the photoelectric transducer film 4.
  • a heterojunction is formed by the intermediate film 3 and the photoelectric transducer film 4.
  • the facts that must be taken into consideration in selecting the material for the intermediate film 3 are (1) that the lattice constant, crystal structure and the coefficient of thermal expansion of the intermediate film approximate those of the photoelectric transducer film and (2) that the band structure of the intermediate film 3 and the photoelectric transducer film are capable of being connected smoothly with each other when they are bonded together. These conditions must be met to improve the photoelectric transducing efficiency by improving the crystal quality of the surface of that side of the photoelectric transducer film from which light enters and thereby reducing the surface state due to lattice defects. Light with a wavelength shorter than one corresponding to the energy band gap of the photoelectric transducer film is absorbed by the photoelectric transducer film at a portion very near its surface. If this portion has a low crystal quality with many recombination centers present in that portion, a low photoelectric transducing-efficiency results.
  • FIG. 2 shows the results of the test in which the characteristic of the photoelectric transducer film 4 of (Zn Cd Te)0 9 (In Tc3)0 05 with the intermediate film 3 of ZnSe is compared with the photoelectric transducer film of the same substance without the intermediate film 3 of ZnSe.
  • curve I is the case without any ZnSe film and curve II with the ZnSe film.
  • curve II associated with the transducer film with the ZnSe film represents a spectral sensitivity for short wavelengths much higher than curve I showing the characteristic of the transducer film in the absence of the ZnSe film. Also, it was found that the use of the ZnSe film reduces the dark current. Further, as a result of comparison, on a replica photograph taken under the electronic microscope, between a first photoelectric transducer element with the intermediate film of ZnSe laid between the glass substrate and the photoelectric transducer film of 500 A. ahd a second photoelectric transducer element without any intermediate film, it was made clear that the grain size of the transducer element with the ZnSe film is larger than that without any ZnSe film.
  • a depositing heater is placed in a depositing means and such a depositing material as ZnS, ZnSe, ZnTe, CdTe, ln Te or their solid solution is applied to the heaters.
  • a solid solution of a desired composition is made.
  • the availability of several heaters permits the manufacture of a composite film without affecting the vacuum condition.
  • a glass substrate with the transparent conductive film attached thereto is heated to 100 to 400C thereby to deposit the solid solution of the above-mentioned composition on it by evaporation.
  • the resulting assembly is heated at 300 to 700C for from several minutes to several hours to produce a photoelectric transducer element.
  • the response to light of an image pickup tube is different from the photoconductive response of an element thereof in principle.
  • the inventors have prepared an equivalent circuit which requires no electron beam, associated with a picture element of the image pickup tube scanned by an electron beam, thereby to evaluate the characteristics of the image pickup tube through an element.
  • the principle of the evaluation is as shown in FIG. 4, in which the photoelectric tube 5 is seen to be turned on and off by a light pulser with a pulse width of 2 us at 60 Hz so as to apply an electron beam to a picture element at 60 Hz.
  • Light of 0.4 lx was radiated on the element from another light source of the halogen lamp of 3,400K so that the responsiveness to light was measured with a shutter usually used for photographing.
  • the results of the measurements mentioned above coincide pretty well with those of measurements conducted on an image pickup tube assembled from the element. The measurements were made in terms of a rise and fall in 50 ms after the application and shutting off the light respectively.
  • composition of the deposited film was measured by solid mass analysis and activation analysis.
  • the characteristics of the image pickup tube were determined as follows:
  • a positive voltage was applied to that side of the image pickup tube to which the transparent conductive film is attached, during the scanning by an electron beam, and a signal current taken out of the transparent conductive film was measured.
  • a lag-image is a transient phenomenon representing the magnitude of a signal current remaining 50 ms after shutting light off. It occurs during the transition stage from a bright to dark state and is generally expressed in the percentage of a signal remaining at a time point 50 ms after shutting light off.
  • An afterimage is a term indicating a time period, as observed by a display monitor, needed for an image of an object to be extinguished on a uniformly white background which was picked up after picking up the object for a predetermined period of time under a standard pickup condition.
  • Embodiments of the present invention will be now explained.
  • Embodiment l
  • a photoelectric transducer element which comprises a heterojunction of an intermediate film of ZnS Se and a photoelectric transducer film of Zn Cd fFe and experiments were conducted by varying the value y of Zn Cd Te while maintaining it of ZnS Se at zero.
  • the assembly comprising a glass substrate 1 with a transparent conductive film 2 deposited on it was heated to and maintained at the temperature of to 400C, andZnSe, that is ZnS,.Se with x at zero, is deposited by evaporation into the thickness of 0.02 to 2 microns on the transparent conductive film 2 for 5 to 30 minutes.
  • ZnSe film 3 On this ZnSe film 3 is formed a solid solution 1 to 20 X 10" m thick by evaporation in a pair of melting pots containing ZnTe and CdTe respectively, while maintaining the temperature of the substrate at 150 to 300C for 5 to 60 minutes.
  • the value of y of the solid solution may be varied by controlling the temperature of the melting pots.
  • the sensitivity of the image pickup tube according to the present invention is 2 or 3 times higher than that of the conventional vidicon. Further, with the increase in the amount of Cd, the sensitivity is improved but the dark current is also increased. There are less lagimage with the increase in the amount of Cd. All this tells that the photoelectric transducer element according to the present invention has a higher sensitivity and a broader range of spectral sensitivity than the Sb S vidicon.
  • Embodiment 2 This embodiment has the same structure as embodiment 1, employing an intermediate film of ZnS Se as in embodiment 1 while it is different from embodiment l in that Zn,Cd1.,,Te with In added thereto is used as a photoelectric transducer film.
  • Zn,Cd1.,,Te with In added thereto is used as a photoelectric transducer film.
  • the amount of In added to the photoelectric transducer film of Zn Cd Te was changed from lXl0"/cc to 2Xl0 /cc, in the presence of an intermediate film of ZnSe, dark current which occurred in the photoelectric transducer element is as shown in Table 2 below From this experiment, it is known that the dark current tends to decrease with'theincrease in the amount of indiumadded to the photoelectric transducer film.
  • the spectral sensitivity for short wavelength can be improved and the range of wavelength over which the sensitivity is effective can be broadened by replacing the intermediate film of ZnSe with a solid solution of ZnS Se
  • the sensitivity may be extended to a desired A wavelength by changing the ratio between Zn and Cd of the photoconductive film.
  • the deposited film was made in the same way as in embodiment l by adding indium to the Zn Cd Te through thermal diffusion and the amount of indium is shown in terms of the quantity placed in an evaporation source.
  • the results of mass analysis show, however, that where a solid solution of Zn Cd Te containing indium in the amount of 2 X lO lcc is used as an evaporation source, 3.2 atomic percent of indium is contained in the deposited film.
  • the deposited film contains 0.02 atomic percent of indium.
  • Embodiment 3 the intermediate filmland the photoelectric transducerfilm respectively as in embodiment 1.
  • the abovementioned image pickup tubes embodying the present invention have a higher sensitivity than the conventional vidicon and PbO vidicon, and the target includedin the embodiments has an almost flat curve of spectral sensitivity over the entire range of visible light, making it possible to apply the present invention to a singletube color image pickup tube.
  • the photoelectric transducer element according to the present invention is high both in photosensitivity and spectral sensitivity, it can be used not only as a target of the image pickup tube but as a photoelectric transducer film for electronic photograph and illumination photometer.
  • the present invention is characterized by a high photosensitivity and spectral sensitivity is the interposition between the transparent conductive film and the photoelectric transducer film of an intermediate film with a larger energy band gap than the photoelectric transducer film, which not only permits the portion sensitive to light, that is, the crystal structure at the junction between the photoelectric transducer film and the intermediate film to be improved but also allows light with a longer wavelength than the one corresponding to the energy band gap of the intermediate film to enter the photoelectric transducer film without loss.
  • the photoelectric transducer element according to the present invention has a higher photosensitivity as well as higher spectral sensitivity without any lag-images, residual images or undesirable after-image.
  • a photoelectric transducer element and a target for an image pickup tube using said element comprising a photoelectric transducer film, a transparent conductive film, a material interposed between said photoelectric transducer film and said transparent conductive film, and a heterojunction of said photoelectric transducer film and said material, said material having a larger energy gap than said photoelectric transducer film, said photoelectric transducer film containing Z n Cdb Te (0.l y0.9) as a main component, and said material containing ZnS,Se,. gxg l) as a main component.
  • a photoelectric transducer element and a target for an image pickup tube using said element comprising a photoelectric transducer film, a transparent conductive film, a material interposed between said photoelectric transducer film and said transparent conductive film, and a heterojunction of said photoelectric transducer film and said material, said material having a larger energy gap than said photoelectric transducer film, said photoelectric transducer film containing Zn Cd Te (0 g y; 1) as a main component and further containing 30 mol percent or less of a compound of In and Te added thereto, said photoelectric transducer film having the formula and said material containing ZnS,,-Se,- ,-(0 5 x 2 l) as a main component.
  • a photoelectric transducer element and a target for an image pickup tube using said element comprising a photoelectric transducer film, a transparent conductive film, a material interposed between said photoelectric transducer film and said transparent conductive film, and a heterojunction of said photoelectric transducer film and said material, said material having a larger energy gap than said photoelectric transducer film, said photoelectric transducer film containing Zn Cd Te (0.5 i y 2 0.8) as a main component and further containing 30 mol percent or less of a compound of ln and Te added thereto, said photoelectric transducer film hhaving the formula and said material containing ZnSe as a main component.
  • a photoelectric transducer element and a target for an image pickup tube using said element comprising a photoelectric transducer film, a transparent conductive film, a material interposed between said photoelectric transducer film and said transparent conductive film, and a heterojunction of said photoelectric transducer film and said material, said material having a larger energy gap than said photoelectric transducer film, said photoelectric transducer film containing Zn Cd Te as a main component and further containing 30 mol percent or less of a compound of [n and Te added thereto, said photoelectric transducer'film having the formula and said material containing ZnSe as a main component.

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  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Light Receiving Elements (AREA)
  • Formation Of Various Coating Films On Cathode Ray Tubes And Lamps (AREA)
US00304050A 1971-11-09 1972-11-06 Photoelectric transducer element including a heterojunction formed by a photoelectric transducer film and an intermediate film having a larger energy gap than the photoelectric transducer film Expired - Lifetime US3858074A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP46089622A JPS5037513B2 (enrdf_load_stackoverflow) 1971-11-09 1971-11-09
JP47003265A JPS5120242B2 (enrdf_load_stackoverflow) 1971-12-29 1971-12-29
JP47096428A JPS524404B2 (enrdf_load_stackoverflow) 1972-09-25 1972-09-25

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US (1) US3858074A (enrdf_load_stackoverflow)
AU (1) AU444944B2 (enrdf_load_stackoverflow)
BE (1) BE791077A (enrdf_load_stackoverflow)
CA (1) CA976265A (enrdf_load_stackoverflow)
DE (1) DE2254605C3 (enrdf_load_stackoverflow)
FR (1) FR2159364B1 (enrdf_load_stackoverflow)
GB (1) GB1393914A (enrdf_load_stackoverflow)
IT (1) IT984638B (enrdf_load_stackoverflow)
NL (1) NL159237B (enrdf_load_stackoverflow)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3985918A (en) * 1972-10-12 1976-10-12 Matsushita Electric Industrial Co., Ltd. Method for manufacturing a target for an image pickup tube
US4589192A (en) * 1984-11-02 1986-05-20 The United States Of America As Represented By The Secretary Of The Army Hybrid epitaxial growth process

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1449956A (en) * 1973-03-30 1976-09-15 Matsushita Electric Industrial Co Ltd Photoconductor element
DE2436990A1 (de) * 1974-08-01 1976-02-12 Bosch Gmbh Robert Fotoleitertarget fuer fernsehaufnahmeroehren mit sperrenden kontakten

Citations (3)

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Publication number Priority date Publication date Assignee Title
US3287611A (en) * 1961-08-17 1966-11-22 Gen Motors Corp Controlled conducting region geometry in semiconductor devices
US3346755A (en) * 1966-03-31 1967-10-10 Rca Corp Dark current reduction in photoconductive target by barrier junction between opposite conductivity type materials
US3405298A (en) * 1965-03-04 1968-10-08 Rca Corp Photoconductive device having a target including a selenium blocking layer

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Publication number Priority date Publication date Assignee Title
BE620887A (enrdf_load_stackoverflow) * 1959-06-18
US3268764A (en) * 1963-01-09 1966-08-23 Westinghouse Electric Corp Radiation sensitive device
US3571646A (en) * 1967-07-17 1971-03-23 Tokyo Shibaura Electric Co Photoconductive target with n-type layer of cadmium selenide including cadmium chloride and cuprous chloride
JPS5027326B1 (enrdf_load_stackoverflow) * 1970-04-22 1975-09-06

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3287611A (en) * 1961-08-17 1966-11-22 Gen Motors Corp Controlled conducting region geometry in semiconductor devices
US3405298A (en) * 1965-03-04 1968-10-08 Rca Corp Photoconductive device having a target including a selenium blocking layer
US3346755A (en) * 1966-03-31 1967-10-10 Rca Corp Dark current reduction in photoconductive target by barrier junction between opposite conductivity type materials

Non-Patent Citations (3)

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Title
Abrikosov et al., Semiconducting II VI, IV VI & V VI, Compounds Plenum press, N.Y., 1969, pp. 26 28, QC612, S4P6. *
Morehead et al., Efficient, Visible Electroluminescence From p n Junctions in Zn Cd TE App. Physics Letters, Vol. 5, 1964, pp. 53 54. *
Tansley, T. L. Heterojunction Properties, Chapt. 6 of Semiconductors & Semimetals, Academic Press, N.Y. & London, 1971, Vol. 7, part A. pp. 299 309 QC612, S4W5. *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3985918A (en) * 1972-10-12 1976-10-12 Matsushita Electric Industrial Co., Ltd. Method for manufacturing a target for an image pickup tube
US4589192A (en) * 1984-11-02 1986-05-20 The United States Of America As Represented By The Secretary Of The Army Hybrid epitaxial growth process

Also Published As

Publication number Publication date
FR2159364B1 (enrdf_load_stackoverflow) 1977-07-29
GB1393914A (en) 1975-05-14
DE2254605B2 (de) 1981-06-19
AU444944B2 (en) 1974-02-07
CA976265A (en) 1975-10-14
IT984638B (it) 1974-11-20
FR2159364A1 (enrdf_load_stackoverflow) 1973-06-22
NL159237B (nl) 1979-01-15
DE2254605C3 (de) 1982-04-15
AU4859272A (en) 1974-02-07
NL7215094A (enrdf_load_stackoverflow) 1973-05-11
DE2254605A1 (de) 1973-05-24
BE791077A (fr) 1973-03-01

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