Patent GB-1070622-A (GB)
Title: Improvements in or relating to methods of manufacturing photo-sensitive devices
IPC: H01J9/233
Filed: 1964-03-10
Abstract: 1,070,622. Semi-conductor devices. PHILIPS ELECTRONIC & ASSOCIATED INDUSTRIES Ltd. March 10, 1964 [March 12, 1963], No. 10053/64. Heading H1K. In the manufacture of a photo-sensitive device of lead monoxide, that part of the active layer to which a negative potential is to be applied in operation is subjected to bombardment with electrically accelerated particles of an acceptor impurity to produce a P-type region giving a low operational dark current. As described this acceptor impurity is oxygen. In making a photo-cell a glass support is provided with two sets of alternately placed electrodes, the electrodes of each set being interconnected. The glass support may temporarily form a wall of an evaporation chamber. Regions of lead monoxide are vapour deposited in an oxygen/argon atmosphere through a mask over one set of electrodes only. These (to be the negative electrodes in operation) consist of tin oxide or vapour-deposited silver. The evaporation chamber is evacuated and refilled at low pressure with oxygen and a direct or alternating potential applied between the coated electrodes and a metal grid spaced from the assembly (the grid is made negative if a direct potential is used) to set up a discharge. The surface of each oxide layer is converted to P-type conductivity by absorbed oxygen. Next a continuous layer of intrinsic or substantially compensated material is evaporated over both sets of electrodes. The second set consist of nickel or platinum. The deposition is carried out in an atmosphere containing oxygen and one or more of water vapour, hydrogen sulphide, hydrogen selenide, and hydrogen telluride. These hydrides act as donors and their anions give the oxide increased red sensitivity. To complete the cell, a cover is sealed to the support and the enclosed space evacuated and preferably refilled with oxygen at low pressure. The cover should be transparent if alternative supports are used which are opaque. In a second embodiment the bulb of a vidicon camera tube is connected to a gas/vacuum system. A transparent tin oxide electrode is formed on the tube window and a layer of lead monoxide deposited on this by evaporation from a H.F.- heated platinum crucible. The deposition takes place in an oxygen/argon atmosphere. The tube window is held at a fixed temperature by a glycerine bath temporarily formed about the window. Bombardment is then carried out in an oxygen atmosphere. The temperature of the film need not be stabilized. The crucible and the sensitive layer, connected through the tin oxide electrode, are used as discharge electrodes. Light may be shone on the layer to make it sufficiently conductive. Instead of the electrode/lead oxide a cylindrical electrode surrounding the crucible may be used as the second discharge electrode. After bombardment the oxygen atmosphere is removed and the layer then exposed to hydrogen sulphide, hydrogen selenide, hydrogen telluride or mixtures thereof. Oxygen bombardment and hydride treatment may be repeated alternately as desired. The process should be terminated by an oxygen bombardment to give the surface exposed to the electron beam in operation a P-type surface layer which, however, should not possess significant lateral conductivity. It is stated that the final layer produced may have, for example, a pi(n)(i)p sequence and that this structure may be repeated if sufficient bombardment/exposure steps are given. The (n) and (i) layers may not be present since their existence depends on the degree of compensation of H 2 X by the oxygen bombardment.