潜影形成过程中的空穴及其转换

doi:10.7517/j.issn.1674-0475.2002.01.46

摘要/Abstract

摘要： 最近几年,在研究卤化银体系的潜影形成效率时,在如何对待和处理光生空穴问题上出现了一些突破传统思路并具有开拓性的方法,我们把它称之为"空穴-电子转换"法.这种方法的关键是寻找或设计一种"化学转换器".这种转换器既能捕获空穴,消除或减少潜影形成过程中由于电子与空穴的复合造成的电子损失,又能经过它的转换产生并释放出额外电子或某种电子载体(如自由基)促进潜影的形成,起到一举两得显著提高卤化银乳剂感光度的作用.本文对当前已有的3种化学转换器的研究进展进行了综合评述,望引起国内科学家的密切关注.

关键词: 分子型化学转换器, 化学增感, 卤化银成像体系

Abstract: In the imaging system of silver halide, photon generated positive holes have been considered as a kind of species which play a negative role to cause inefficiency of latent image formation via recombination with electrons, regressive reaction with silver clusters and so on. Recently, some kind of novel sensitization technique that might be called as a conversion of hole to electron has been developed and are greatly interested in. So far 3 kinds of compounds have been found to act as a chemical converter. These are: 1) silver dimmer (Ag₂); 2) compounds of carboxylic acids including formic acid; 3)FED compounds, i.e fragmentable two electron donors. Each of these compunds possesses two elementary functions: trapping hole and releasing an extra electron through conversion when it is adsorbed or introduced into silver halide crystals. In this paper, features, mechanism and effect etc. of these converters are reviewed.

Key words: molecular type of chemical converters, chemical sensitization, imaging system of silver halide

中图分类号:

TQ57

夏培杰, 国红, 姚林辉, 赵文芳. 潜影形成过程中的空穴及其转换[J]. 影像科学与光化学, 2002, 20(1): 46-59.

XIA Pei-jie, GUO Hong, YAO Lin-hui, ZHAO Wen-fang. CONVERSION OF POSITIVE HOLE TO ELECTRON IN THE PROCESS OF LATENT IMAGE FORMATION[J]. Imaging Science and Photochemistry, 2002, 20(1): 46-59.

参考文献

[1] Bird D R, Jones R C, Ames A E. The efficiency of radiation detection by photographic films: state-of-the-art and methods of improvement[J]. Appl. Optics, 1969, 8(12):2389-2405.
[2] Tani T. In: Photography Sensitivity (Theory and Mechanisms)[M]. Chapter 8. New York: Oxford Uni. Press, 1995.
[3] Harbison J M, Spencer H E. Chemical sensitization and environmental effects. In: James T H. The Theory of the Photographic Process[M]. Chapter 5, 4th ed. New York: Macmillian, 1977.
[4] Spencer H E, Brady L E, Hamilton J F. Distributions of development centers in reduction-sensitized silver bromide grains[J]. J. Opt. Soc. Am., 1967, 57(8): 1020.
[5] Spencer H E. Reactions of electrons and holes in latent-image formation[J]. Photogr. Sci. Eng., 1967, 11:352.
[6] Tani T. Photographic effects of electron and positive hole traps I. Chemical sensitization, reducing agents and phenosafranine[J]. Photogr. Sci. Eng., 1971, 15:28.
[7] Tani T. Photographic effects of electron and positive hole traps in silver halide Ⅱ. Reduction sensitization in octahedral silver halide grains[J]. Photogr. Sci. Eng., 1971, 15(3):181.
[8] Tani T. Photographic effects of electron and positive hole traps in silver halide Ⅳ. Reduction sensitization in various silver bromide grains[J]. Photogr.Sci. Eng., 1972. 16(1):35.
[9] Tani T. Photographic effects of electron and positive hole traps in silver halide Ⅶ. Interaction between reduction sensitization and desensitization by dye on various silver bromide grains[J]. Photogr. Sci. Eng., 1974, 18(5):569.
[10] Collier S S.Speed and fog increases from the addition of surface reduction sensitization to a surface sulfur-plus-gold sensitized 1- μm AgBr octahedral emulsion[J].Photogr.Sci.Eng.,1982,26:98.
[11] Vanassche W, Borginon H, Pattyn H, et al. Emulsion characteristics influencing the photographic response of hole trapping by reduction sensitization centers [J].J. Photogr. Sci.,1974, 22(3):121.
[12] Moisar E, Granzer F, Dautrich D, et al. Formation and properties of sub-image and latent-image silver specks part I: Thermodynamics of silver speck formation[J]. J. Photogr. Sci., 1977, 25(1):12.
[13] Palm E, Granzer F, Moisar E, et al. Formation and properties of sub-image and latent-image silver specks part Ⅱ: Properties of silver sub-specks produces by chemical reduction[J]. J. Photogr. Sci., 1977, 25(1):19.
[14] Dautrich D, Granzer F, Moisar E, et al. Formation and properties of sub-image and latent-image silver specks part Ⅲ: Properties of silver sub-specks produces by radiation[J].J. Photogr. Sci., 1977, 25:169.
[15] Moisar E, Granzer F, Dautrich D, et al. Formation and properties of sub-image and latent-image silver specks part Ⅳ: The formation of silver specks-A process of nucleation and phase formation[J]. J. Photogr. Sci., 1980, 28:71.
[16] Hamilton J F, Baetzold R C. The paradox of Ag2 centers on AgBr: reduction sensitization vs. photolysis.[J]. Photogr. Sci. Eng., 1981, 25:189.
[17] Tani T, Murofushi M. Silver microclusters on silver halide grains as latent image and reduction sensitization centers[J]. J. Imaging Sci. and Tech., 1994, 38(1):1.
[18] Tani T. Silver clusters of photographic interest (2): A new model for r and p centers[J].J. Imaging Sci. and Tech., 1997, 41:577-588.
[19] Herz A H, Danner R P, Janusonis G A. In: Adsorption from Aqueous Solution (Advances in Chemistry), Series 79)[M]. Washington D C: American Chemical Society, 1968. 173.
[20] Babcock T A, James T H. Use of hydrogen hypersensitization to diminish recombination and produce emulsion coating of high quantum efficiency[J]. J. Photogr. Sci., 1976, 24:19.
[21] Hailstone R K, Liebert N B, Levy M, et al. Achieving high quantum sensitivities with hydrogen hypersensitization 1. Measurement[J]. J. Imaging Sci., 1988, 32:113.
[22] Tani T. Silver clusters of photographic interest Ⅳ: Reduction sensitization of silver chloride and silver bromide emulsions[J]. J.Imaging Sci. and Tech., 1998, 42:402.
[23] Lowe W G. In: James T H. The Theory of the Photographic Proces[M]. Chapter 5, 4th Ed. New York: Macmillan, 1977, 152.
[24] Tani T. A study of intensification of latent imagesin reduction-sensitized emulsions through delayed development[J]. J. Imaging Sci., 1986, 30(2):41.
[25] Hailstone R K, Liebert N B, Levy M, et al. Achieving high quantum sensitivities with hydrogen hypersensitization 2. Mechanism[J]. J. Imaging Sci., 1991,35:219.
[26] Tani T, Tasaka T, Murofushi M, et al. Silver clusters of photographic interest part 5: formation of R centers and P centers by reduction sensitization and light absorption of silber bromide grains[J]. J. Imaging Sci., 1999, 47:1.
[27] Tani T. Analysis of factors influencing photographic sensitivity[J]. J. Imaging Sci., 1985, 29(3):93.
[28] Kamat P V. Photochemistry on nonreactive and reactive (semiconductor) surface[J]. Chemical Review, 1993, 93(1):267.
[29] Jaeger C D, Bard A J. Spin trapping and electron spin resonance detection of radical intermediates in the photodecomposition of water at TiO₂particulate systems[J]. J. Phys. Chem., 1979, 83(24):3146.
[30] Harbour J R, Hair M L. Radical intermediates in the photosynthetic generation of H₂O₂with aqueous ZnO dispersions[J]. J. Phys. Chem., 1979, 83(6):652.
[31] 陈次平,任新民.自旋捕捉技术在多相体系光反应中的应用[J].感光科学与光化学,1989,(3):56.Chen C P, Ren X M. Application of the technique of spin trapping in photo-reactions of multiphase systems[J]. Photographic Science and Photochemistry, 1989, (3):56.
[32] 陈次平,任新民,陆道惠,等.乙酸钠、草酸钠、酒石酸钾在三氧化钨-水体系中光生自由基的研究[J].感光科学与光化学,1991,9(4):299.Chen C P, Ren X M,Lu D H,et al. ESR study on photogenerated radicals in aqueous dispersions of tungsten oxide containing sodium acetate, sodium oxalate and potassium tartrate[J]. Photographic Science and Photochemistry, 1991, 9(4):299.
[33] De Keyzer R, Treguer M, Belloni-Cofler J,et al. A photosensitive silver halide element with increased photosensitivity[P]. EP 0 922 994 A2. 1998-11-30.
[34] Belloni J, Treguer M, Remita H, et al. Enhanced yield of photoinduced electrons in doped silver halide crystals[J].Nature, 1999, 402:865.
[35] Silberstein L. On the number of quanta required for the developability of a silver halide grain[J]. J. Opt. Soc. Am., 1941, 31:343.
[36] Hailstone R. Making every photon count[J]. Nature, 1999, 402:856.
[37] Rao P S, Hayon E. Redox potentials of free radicals Ⅲ. Reevaluation of the method[J]. J. Am. Chem. Soc., 1975, 97(11):2986
[38] Wayner D D, McPhee D J, Griller D. Oxidation and reduction potentials of transient free radicals[J]. J. Am. Chem. Soc., 1988, 110(1):132.
[39] Su Z, Mariano P S, Falvey D E, et al. Dynamics of anilinium radical α-heterolytic fragmentation process. electrofugal group, substituent, and medium effects on desilytation, decarboxylation, and retro-aldol cleavage pathways[J].J. Am. Chem. Soc., 1998, 120:10676.