reactions revealed by in situ X ray nanodiffraction fileThe Gurney-Mott theory was later modified by Hedges and Mitchell. 6. to include chemical sensitizers or impurities that can

$Page 1: reactions revealed by in situ X ray nanodiffraction fileThe Gurney-Mott theory was later modified by Hedges and Mitchell. 6. to include chemical sensitizers or impurities that can$
SUPPLEMENTARY INFORMATIONDOI: 10.1038/NMAT4311

NATURE MATERIALS | www.nature.com/naturematerials 1

1

SUPPLEMENTARY INFORMATION

Grain rotation and lattice deformation during photoinduced chemical

reactions revealed by in situ X-ray nanodiffraction

Zhifeng Huang1§, Matthias Bartels2, Rui Xu1, Markus Osterhoff2, Sebastian Kalbfleisch2,

Michael Sprung3, Akihiro Suzuki5, Yukio Takahashi5, Thomas N. Blanton4†, Tim Salditt2 and

Jianwei Miao1*

1Department of Physics & Astronomy and California NanoSystems Institute, University of

California, Los Angeles, CA 90095, USA. 2Institut für Röntgenphysik, Georg-August-Universität

Göttingen, Friedrich-Hund-Platz 1, 37077 Göttingen, Germany. 3DESY, Notkestr. 85, 22607

Hamburg, Germany. 4Kodak Technology Center, Eastman Kodak Company, Rochester, NY

14650-2106, USA. 5Department of Precision Science and Technology, Graduate School of

Engineering, Osaka University, 2-1 Yamada-oka, Suita, Osaka 565-0871, Japan. §Present

affiliation: Carl ZEISS X-ray Microscopy Inc., Pleasanton, CA 94588, USA. †Present affiliation:

International Centre for Diffraction Data, Newtown Square, PA 19073, USA. *Correspondence and requests for materials should be addressed to J.M.

([email protected]).

Supplementary Text: The mechanism of the photographic process

AgBr is a unique and basic light-sensitive material in photochemistry and modern photographic industries1-3. The first accepted mechanism explaining latent image formation was proposed by Gurney and Mott in 1938 (ref. 4). Using a crystal lattice of AgBr as an example, Ag is positively charged (Ag+) and Br is negatively charged (Br-). When a photon of sufficient energy is absorbed, an electron is released from the Br ion, creating a neutral Br atom and a free electron. The electron is mobile and can move through the crystal until it becomes trapped by a potential latent image site (i.e. dislocation) creating a negatively charged trap. This step is referred to as the electronic conduction stage. The negative charge attracts Ag+ ions which migrate through the crystal via interstitial positions, creating a Ag0 atom. The result is that the

Grain rotation and lattice deformation during photoinduced chemical reactions revealed by in situ X-ray nanodiffraction

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http://dx.doi.org/10.1038/nmat4311

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SUPPLEMENTARY INFORMATION DOI: 10.1038/NMAT4311

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trap becomes charge neutral. This second step is the ionic conduction stage. The process can repeat multiple times creating an aggregation of Ag atoms. The resulting neutral halogen eventually migrates to the AgBr crystal surface by a process of electron transfer5. This halide while internal to the grain is referred to as a positive hole. The Gurney-Mott theory was later modified by Hedges and Mitchell6 to include chemical sensitizers or impurities that can create a different type of trap present in a AgBr grain. These sensitizers act as positive hole traps that prevent a recombination of the neutral halogens with electrons, allowing the electrons to migrate to lattice defects for latent image formation.

In traditional photographic theories, the visible-light-induced latent image Ag site acts as a catalyst that allows for the preferential reduction of exposed AgBr grains to form Ag0 via chemical developers such as hydroquinone7. But the formation of a submicroscopic latent image silver sites due to X-ray exposure is not the result of the X-ray photon itself but instead an interaction resulting in the production of secondary charged particles. For example, these interactions can occur by photoelectric or Compton effects as a result of absorption or scattering of the X-ray photon8. In a typical reaction of AgBr with visible light, AgBr grains are surface sensitized such that exposure to visible light preferentially causes Ag0 development centers to form on the grain surfaces. In AgBr photolysis with X-rays, the silver latent image site grows to become a silver speck and can be found internal to the grain or on the grain surface. Continued high-energy radiation exposure can result in filaments or dendrites growing from the surface of the AgBr grain9,10. This process is generally not very efficient for short time X-ray irradiation such as a medical X-ray, so a visible light emitting phosphor is placed next to the X-ray film to increase exposure efficiency. But in our current experiment, it is not a problem because of ultra-high intensity and relatively long-time exposure. However, the efficiency of X-ray absorption by AgBr is in the range of 3-10% depending on the total AgBr chemistry and X-ray energy.

The face diagonal of the Ag0 lattice (5.779Å) is almost the same length as the cube edge length of AgBr (5.774Å) resulting in two observed orientations of Ag0 relative to the host AgBr. The first is {100} faces parallel and rotated 45 about the <100> axis. The second is {110} faces parallel and rotated 90 about the [100] axis. The mechanism of photolytic Ag formation requires a net mass transport to the Ag aggregate. The resulting strain in the AgBr lattice is relieved as the Ag0 particle(s) grow by continuous generation of prismatic dislocation loops, that move along the <110> glide plane11.

In experiments using laboratory source UV (1-3 h) or X-ray (45 min) exposure of AgBr single crystals, Berry and Griffith12 observed X-ray diffraction Weissenberg patterns change from spots for the AgBr phase in the initial neat single crystal, to rings due to AgBr and Ag0 randomly oriented crystallites after extended UV or X-ray exposure. A similar result was observed for AgI exposed to ambient light, with the single crystal fragmenting into a mosaic structure due to strains produced as photolytic Ag0 is formed5. Convergent beam X-ray analysis was used to identify the mosaic structure of precipitated AgBr grains12. As latent imaging sites grow in size due to Ag0 atom agglomeration in different locations within a grain, inhomogeneous strain due to changes in lattice spacing were found to be present. If this strain exceeds elastic deformation, a crystal can fragment into a polycrystalline sample.

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Supplementary Figures

Supplementary Figure 1. Stability test of the nano-focused in situ XRD system. Real-time measurements of the XRD patterns from a 12.5-m-thick Ag film as a function of the exposure time, indicating that the in situ system itself does not contribute to grain rotation or lattice deformation. Color bar: logarithmic scale with an arbitrary unit (same for Supplementary Figs. 3, 4, 6 and 7).





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trap becomes charge neutral. This second step is the ionic conduction stage. The process can repeat multiple times creating an aggregation of Ag atoms. The resulting neutral halogen eventually migrates to the AgBr crystal surface by a process of electron transfer5. This halide while internal to the grain is referred to as a positive hole. The Gurney-Mott theory was later modified by Hedges and Mitchell6 to include chemical sensitizers or impurities that can create a different type of trap present in a AgBr grain. These sensitizers act as positive hole traps that prevent a recombination of the neutral halogens with electrons, allowing the electrons to migrate to lattice defects for latent image formation.

In traditional photographic theories, the visible-light-induced latent image Ag site acts as a catalyst that allows for the preferential reduction of exposed AgBr grains to form Ag0 via chemical developers such as hydroquinone7. But the formation of a submicroscopic latent image silver sites due to X-ray exposure is not the result of the X-ray photon itself but instead an interaction resulting in the production of secondary charged particles. For example, these interactions can occur by photoelectric or Compton effects as a result of absorption or scattering of the X-ray photon8. In a typical reaction of AgBr with visible light, AgBr grains are surface sensitized such that exposure to visible light preferentially causes Ag0 development centers to form on the grain surfaces. In AgBr photolysis with X-rays, the silver latent image site grows to become a silver speck and can be found internal to the grain or on the grain surface. Continued high-energy radiation exposure can result in filaments or dendrites growing from the surface of the AgBr grain9,10. This process is generally not very efficient for short time X-ray irradiation such as a medical X-ray, so a visible light emitting phosphor is placed next to the X-ray film to increase exposure efficiency. But in our current experiment, it is not a problem because of ultra-high intensity and relatively long-time exposure. However, the efficiency of X-ray absorption by AgBr is in the range of 3-10% depending on the total AgBr chemistry and X-ray energy.

The face diagonal of the Ag0 lattice (5.779Å) is almost the same length as the cube edge length of AgBr (5.774Å) resulting in two observed orientations of Ag0 relative to the host AgBr. The first is {100} faces parallel and rotated 45 about the <100> axis. The second is {110} faces parallel and rotated 90 about the [100] axis. The mechanism of photolytic Ag formation requires a net mass transport to the Ag aggregate. The resulting strain in the AgBr lattice is relieved as the Ag0 particle(s) grow by continuous generation of prismatic dislocation loops, that move along the <110> glide plane11.

In experiments using laboratory source UV (1-3 h) or X-ray (45 min) exposure of AgBr single crystals, Berry and Griffith12 observed X-ray diffraction Weissenberg patterns change from spots for the AgBr phase in the initial neat single crystal, to rings due to AgBr and Ag0 randomly oriented crystallites after extended UV or X-ray exposure. A similar result was observed for AgI exposed to ambient light, with the single crystal fragmenting into a mosaic structure due to strains produced as photolytic Ag0 is formed5. Convergent beam X-ray analysis was used to identify the mosaic structure of precipitated AgBr grains12. As latent imaging sites grow in size due to Ag0 atom agglomeration in different locations within a grain, inhomogeneous strain due to changes in lattice spacing were found to be present. If this strain exceeds elastic deformation, a crystal can fragment into a polycrystalline sample.

3

Supplementary Figures

Supplementary Figure 1. Stability test of the nano-focused in situ XRD system. Real-time measurements of the XRD patterns from a 12.5-m-thick Ag film as a function of the exposure time, indicating that the in situ system itself does not contribute to grain rotation or lattice deformation. Color bar: logarithmic scale with an arbitrary unit (same for Supplementary Figs. 3, 4, 6 and 7).





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Supplementary Figure 2. a, SEM image of a Kodak linagraph paper (Type 2167) before exposure to X-rays, showing relatively large AgBr grains (~1-3 μm in size) on the surface. Scale bar: 1μm. b, SEM image of the cross section of the linagraph paper with FIB, showing smaller AgBr grains (~700 nm in size) dispersed in gelatin. Scale bar: 1μm. c, SEM image of the zoomed region (yellow rectangle) in (b), showing several AgBr grains of ~700 nm in size. Scale bar: 200 nm.

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Supplementary Figure 3. a, XRD pattern of the average intensity from Supplementary Movie 1, showing Debye-Scherrer rings of various materials in a Kodak linagraph paper. b, Conventional XRD profile of a Kodak linagraph paper with =1.5418Å, showing the diffraction spots of various materials in the sample.





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Supplementary Figure 2. a, SEM image of a Kodak linagraph paper (Type 2167) before exposure to X-rays, showing relatively large AgBr grains (~1-3 μm in size) on the surface. Scale bar: 1μm. b, SEM image of the cross section of the linagraph paper with FIB, showing smaller AgBr grains (~700 nm in size) dispersed in gelatin. Scale bar: 1μm. c, SEM image of the zoomed region (yellow rectangle) in (b), showing several AgBr grains of ~700 nm in size. Scale bar: 200 nm.

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Supplementary Figure 3. a, XRD pattern of the average intensity from Supplementary Movie 1, showing Debye-Scherrer rings of various materials in a Kodak linagraph paper. b, Conventional XRD profile of a Kodak linagraph paper with =1.5418Å, showing the diffraction spots of various materials in the sample.





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Supplementary Figure 4. Real-time observation of the photolysis of AgBr grains and photoinduced grain rotation in a controlled sample (AgBr/membrane). Four representative diffraction patterns excerpted from Supplementary Movie 2 at 0, 2.34, 4.29 and 9.75 sec., respectively (temporal resolution: 130 ms).

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Supplementary Figure 5. a, SEM image of a Kodak linagraph paper after exposed to X-rays. Scale bar: 1μm. b, Zoomed view of the rectangular region in (a), showing filamentary Ag structures (arrows). Scale bar: 100 nm. c and d, SEM images of controlled samples (AgBr/membrane), showing filamentary Ag structures (arrows). Scale bar: 1μm.





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Supplementary Figure 4. Real-time observation of the photolysis of AgBr grains and photoinduced grain rotation in a controlled sample (AgBr/membrane). Four representative diffraction patterns excerpted from Supplementary Movie 2 at 0, 2.34, 4.29 and 9.75 sec., respectively (temporal resolution: 130 ms).

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Supplementary Figure 5. a, SEM image of a Kodak linagraph paper after exposed to X-rays. Scale bar: 1μm. b, Zoomed view of the rectangular region in (a), showing filamentary Ag structures (arrows). Scale bar: 100 nm. c and d, SEM images of controlled samples (AgBr/membrane), showing filamentary Ag structures (arrows). Scale bar: 1μm.





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Supplementary Figure 6. Real-time observation of photoinduced simultaneous lattice deformation and grain rotation in a Kodak linagraph paper. a, An XRD pattern averaged from real-time measurements of the Kodak linagraph paper (Supplementary Movies 4 and 5, temporal resolution: 29 ms). b, A track image and 6 representative frames of the rectangular region in (a) from Supplementary Movie 5. The track image shows the trajectory of a moving diffraction spot between 15.54 sec. to 16.39 sec., where arrows show the motion of the spot. c, Quantification of the lattice deformation and grain rotation of the rectangular region in (a) between 15.54 sec. to 16.39 sec., where labels (a)-(g) correspond to those in (b).

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Supplementary Figure 7. Other examples on real-time observation of photoinduced simultaneous lattice deformation and grain rotation in a Kodak linagraph paper. a, An XRD pattern averaged from real-time measurements of a Kodak linagraph paper (Supplementary Movies 7 and 8, temporal resolution: 140 ms). b, A ROI image of the red rectangular region in (a) and 6 representative frames from Supplementary Movie 7. The representative images show the trajectories of a moving diffraction spot between 12.32 and 13.01 sec., where arrows show the motion of the spot. c, A ROI image of the black rectangular region in (a) and 6 representative frames of Supplementary Movie 8. The representative images show the trajectories of a moving diffraction spot between 23.66 and 24.36 sec., where arrows show the motion of the spot.





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Supplementary Figure 6. Real-time observation of photoinduced simultaneous lattice deformation and grain rotation in a Kodak linagraph paper. a, An XRD pattern averaged from real-time measurements of the Kodak linagraph paper (Supplementary Movies 4 and 5, temporal resolution: 29 ms). b, A track image and 6 representative frames of the rectangular region in (a) from Supplementary Movie 5. The track image shows the trajectory of a moving diffraction spot between 15.54 sec. to 16.39 sec., where arrows show the motion of the spot. c, Quantification of the lattice deformation and grain rotation of the rectangular region in (a) between 15.54 sec. to 16.39 sec., where labels (a)-(g) correspond to those in (b).

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Supplementary Figure 7. Other examples on real-time observation of photoinduced simultaneous lattice deformation and grain rotation in a Kodak linagraph paper. a, An XRD pattern averaged from real-time measurements of a Kodak linagraph paper (Supplementary Movies 7 and 8, temporal resolution: 140 ms). b, A ROI image of the red rectangular region in (a) and 6 representative frames from Supplementary Movie 7. The representative images show the trajectories of a moving diffraction spot between 12.32 and 13.01 sec., where arrows show the motion of the spot. c, A ROI image of the black rectangular region in (a) and 6 representative frames of Supplementary Movie 8. The representative images show the trajectories of a moving diffraction spot between 23.66 and 24.36 sec., where arrows show the motion of the spot.





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Supplementary Figure 8. Average of ten 1D curves, each of which was azimuthally summed from a frame in Supplementary Movie 1 (frames #14, #18, #22, #26, #30, #34, #38, #42, #46 and #50). The Ag(111), AgBr(220)/Ag(200), AgBr(200) and AgBr(111) peak positions agree with the known lattice spacing values as indicated by the arrows.

Supplementary Movies Supplementary Movie 1. Real-time measurements of photolysis and photoinduced grain rotation in a Kodak linagraph paper during exposure to X-rays. The XRD patterns are collected by a PILATUS 1M detector in the full-frame mode (temporal resolution: 140 ms). Supplementary Movie 2. Real-time measurements of photolysis, photoinduced grain rotation and lattice deformation in a controlled AgBr sample (AgBr/membrane) during exposure to X-rays. The XRD patterns are collected by a PILATUS 6M detector in the full-frame mode (temporal resolution: 130 ms). Rectangles are used to indicate the simultaneous grain rotation and lattice deformation. Supplementary Movie 3. Real-time measurements of photoinduced grain rotation in a Kodak linagraph paper during exposure to X-rays. The XRD patterns were collected by a PILATUS 1M detector in the 1-module mode (temporal resolution: 5 ms). The Supplementary Movie is slowed down by 20 times in order to visualize the effect.

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Supplementary Movies 4 and 5. Two separate clips of the real-time measurements of photolysis, photoinduced grain rotation and lattice deformation in a Kodak linagraph paper during exposure to X-rays. The XRD patterns are collected by a PILATUS 1M detector in the 3-module mode (temporal resolution: 29 ms). Rectangles are used to indicate the simultaneous grain rotation and lattice deformation. Supplementary Movie 6. Real-time measurements of photolysis, photoinduced grain rotation and lattice deformation in a controlled AgBr sample (AgBr/membrane) during exposure to X-rays. The XRD patterns are collected by a PILATUS 6M detector in the full-frame mode (temporal resolution: 130 ms). A rectangle is used to indicate the simultaneous grain rotation and lattice deformation. Supplementary Movies 7 and 8. Two separate clips of the real-time measurements of photolysis, photoinduced grain rotation and lattice deformation in a Kodak linagraph paper during exposure to X-rays. The XRD patterns are collected by a PILATUS 1M detector in the full-frame mode (temporal resolution: 140 ms). Rectangles are used to indicate the simultaneous grain rotation and lattice deformation.

References 1. Mees, C. E. K. Recent advances in our knowledge of the photographic process. Publ. Astron.

Soc. Pac. 54, 176-184 (1942). 2. Hamilton, J. F. The silver halide photographic process. Adv. Phys. 37, 359-441 (1988). 3. Eachus, R. S., Marchetti, A. P. & Muenter, A. A. The photophysics of silver halide imaging

materials. Annu. Rev. Phys. Chem. 50, 117-44 (1999). 4. Gurney, R. W. & Mott, N. F. The theory of the photolysis of silver bromide and the

photographic latent image. Proc. R. Soc. London A 64, 151-167 (1938). 5. Burley, G. Photolytic behavior of silver iodide. J. Res. Nat. Bur. Std. – A. Phys. Chem. 67A,

301-307 (1963). 6. Hedges, J. M. & Mitchell, J. W. Some experiments on photographic sensitivity. Phil. Mag.

44, 357-388 (1953). 7. Lee, W. E. & Brown, E. R. The developing agents and their reactions, in The Theory of the

Photographic Process, James, T.H. Ed. (Macmillan Publishing Co., Inc., New York, 1977) pp. 298-300. [4th edition]

8. Bromley, D. & Herz, R. H. Quantum Efficiency in Photographic X-ray Exposures. Proc. Phys. Soc. London, Sect. B 63, 90-106 (1950).

9. Berry, C.R. Growth of silver filaments and dendrites, J. Opt. Soc. Amer. 40, 615-617, (1950). 10. Ohachi, T. & Taniguchi, I. Controlled filamentary growth of silver from silver compounds. J.

Cryst. Growth 13/14, 191-197(1972). 11. Hamilton, J. F. & Brady, L. E. Print‐out process in photographic emulsion grains. J. Appl.

Phys. 31, 609-610 (1960). 12. Berry, C. R. & Griffith, R. L. Structure and growth mechanism of photolytic silver in silver

bromide. Acta. Cryst. 3, 219-222 (1950).





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Supplementary Figure 8. Average of ten 1D curves, each of which was azimuthally summed from a frame in Supplementary Movie 1 (frames #14, #18, #22, #26, #30, #34, #38, #42, #46 and #50). The Ag(111), AgBr(220)/Ag(200), AgBr(200) and AgBr(111) peak positions agree with the known lattice spacing values as indicated by the arrows.

Supplementary Movies Supplementary Movie 1. Real-time measurements of photolysis and photoinduced grain rotation in a Kodak linagraph paper during exposure to X-rays. The XRD patterns are collected by a PILATUS 1M detector in the full-frame mode (temporal resolution: 140 ms). Supplementary Movie 2. Real-time measurements of photolysis, photoinduced grain rotation and lattice deformation in a controlled AgBr sample (AgBr/membrane) during exposure to X-rays. The XRD patterns are collected by a PILATUS 6M detector in the full-frame mode (temporal resolution: 130 ms). Rectangles are used to indicate the simultaneous grain rotation and lattice deformation. Supplementary Movie 3. Real-time measurements of photoinduced grain rotation in a Kodak linagraph paper during exposure to X-rays. The XRD patterns were collected by a PILATUS 1M detector in the 1-module mode (temporal resolution: 5 ms). The Supplementary Movie is slowed down by 20 times in order to visualize the effect.

11

Supplementary Movies 4 and 5. Two separate clips of the real-time measurements of photolysis, photoinduced grain rotation and lattice deformation in a Kodak linagraph paper during exposure to X-rays. The XRD patterns are collected by a PILATUS 1M detector in the 3-module mode (temporal resolution: 29 ms). Rectangles are used to indicate the simultaneous grain rotation and lattice deformation. Supplementary Movie 6. Real-time measurements of photolysis, photoinduced grain rotation and lattice deformation in a controlled AgBr sample (AgBr/membrane) during exposure to X-rays. The XRD patterns are collected by a PILATUS 6M detector in the full-frame mode (temporal resolution: 130 ms). A rectangle is used to indicate the simultaneous grain rotation and lattice deformation. Supplementary Movies 7 and 8. Two separate clips of the real-time measurements of photolysis, photoinduced grain rotation and lattice deformation in a Kodak linagraph paper during exposure to X-rays. The XRD patterns are collected by a PILATUS 1M detector in the full-frame mode (temporal resolution: 140 ms). Rectangles are used to indicate the simultaneous grain rotation and lattice deformation.

References 1. Mees, C. E. K. Recent advances in our knowledge of the photographic process. Publ. Astron.

Soc. Pac. 54, 176-184 (1942). 2. Hamilton, J. F. The silver halide photographic process. Adv. Phys. 37, 359-441 (1988). 3. Eachus, R. S., Marchetti, A. P. & Muenter, A. A. The photophysics of silver halide imaging

materials. Annu. Rev. Phys. Chem. 50, 117-44 (1999). 4. Gurney, R. W. & Mott, N. F. The theory of the photolysis of silver bromide and the

photographic latent image. Proc. R. Soc. London A 64, 151-167 (1938). 5. Burley, G. Photolytic behavior of silver iodide. J. Res. Nat. Bur. Std. – A. Phys. Chem. 67A,

301-307 (1963). 6. Hedges, J. M. & Mitchell, J. W. Some experiments on photographic sensitivity. Phil. Mag.

44, 357-388 (1953). 7. Lee, W. E. & Brown, E. R. The developing agents and their reactions, in The Theory of the

Photographic Process, James, T.H. Ed. (Macmillan Publishing Co., Inc., New York, 1977) pp. 298-300. [4th edition]

8. Bromley, D. & Herz, R. H. Quantum Efficiency in Photographic X-ray Exposures. Proc. Phys. Soc. London, Sect. B 63, 90-106 (1950).

9. Berry, C.R. Growth of silver filaments and dendrites, J. Opt. Soc. Amer. 40, 615-617, (1950). 10. Ohachi, T. & Taniguchi, I. Controlled filamentary growth of silver from silver compounds. J.

Cryst. Growth 13/14, 191-197(1972). 11. Hamilton, J. F. & Brady, L. E. Print‐out process in photographic emulsion grains. J. Appl.

Phys. 31, 609-610 (1960). 12. Berry, C. R. & Griffith, R. L. Structure and growth mechanism of photolytic silver in silver

bromide. Acta. Cryst. 3, 219-222 (1950).



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reactions revealed by in situ X ray nanodiffraction fileThe Gurney-Mott theory was later modified by Hedges and Mitchell. 6. to include chemical sensitizers or impurities that can