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Home , Color, Daguerreotype, Silver halide

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Catherine by Edited and 87131; NM Albuquerque, Mexico, a nraE Schlather E. Andrea daguerreotypes of properties plasmonic The nanotechnology: Nineteenth-century www.pnas.org/cgi/doi/10.1073/pnas.1904331116 eateto cetfi eerh h erpltnMsu fAt e ok Y10028; NY York, New Art, of Museum Metropolitan The Research, Scientific of Department rmteps.Frcnuis epesace o increasingly for searched relic people a centuries, like For seem past. can the prints photographic from age, digital today’s n w etre ae,teei uhfcso engineering on focus much is there later, centuries Two | plasmon a | alGieri Paul , oo printing color c etr akom oot,O 4 S,Canada 2S1, M4M ON Toronto, , Century b ieRobinson Mike , | ea nanoparticle metal ´ Daguerre e c | ivaA Centeno A. Silvia , nssrsosbefrterotclrsos.T hsdate, this To mech- response. chemical optical an and their requires which physical for posterity, the responsible for of anisms preserved understanding be in-depth must that resemble ture devices these Indeed, of consid- printing. fabrication be color (35). the the plasmonic daguerreotypy can for with of daguerreotypes proposals realization significantly novel , first change this the can ered In and angle. dynamic daguerreo- viewing also a of are tones image the type uniquely, Metropolitan Quite The Art. 1 of of of collection Museum Fig. study density in the the from seen daguerreotype on cal be depending can respectively, midtones as tones, the dark nanostructures, of and behavior bright the the reflection with creates specular substrate the the and nanostructures of the the between by balance scattered The that substrate. light image silver an reflective a create off to projects nanoparticles metallic by 34). scattering (33, light pottery since and glass used is to been color there provide have to Indeed, nanostructures times (30–32). ancient metal that applications evidence printing clear color with for plat- ideal along form an nanostructures This, plasmonic makes limit resolution, (29). subdiffraction spatial and illuminated simplicity, material fre- is durability, long-term resonant nanostructure scattered and the plasmon absorbed are when the which hence dictate and quency composition light, its material morphology with determine nanostructure’s and the nanostructure interaction Furthermore, metallic surface strong response. a as optical their by known to supported oscillations Due plasmons collective 28). to (27, rise plasmons giving light, to ulse nieJn 0 2019. 10, June online Published 1 13724.y page on Commentary See the under Published Submission.y Direct PNAS a is article paper. y This interest.y the of wrote conflict A.M. no and declare S.A.C., authors M.R., P.G., The A.E.S., and data; analyzed M.R., P.G., A.M. and A.E.S., and S.A.C., tools; P.G., reagents/analytic S.A.C., new A.E.S., contributed research; M.R. designed research; performed A.M. A.M. and S.A.C., A.E.S., contributions: Author owo orsodnemyb drse.Eal [email protected] Email: addressed. be may correspondence whom To rnig hr aotutrsaedrcl auatrdby manufactured color directly light. are for nanostructures approaches in where additional printing, therefore, preser- inspire developing can and for protocols, artworks insight vation valuable these the providing to of of addition understanding effects scientific optical a unique provide nano- results daguerreotype Our these the image. of of material characteristics the dimensions the determine structures how and on morphology, analysis composition, theoretical detailed a and provide we experimental Here surface. their metal- on by produced nanostructures scattering lic light to range resolu- dynamic image and properties, tion, optical 19th incredible the their of owe century, photographs earliest the among Daguerreotypes, Significance auretpsaeirpaebercrso itr n cul- and history of records irreplaceable are Daguerreotypes on rely photographs, of types other unlike Daguerreotypes, a n ljnr Manjavacas Alejandro and , b eateto hsc n srnm,Uiest fNew of University Astronomy, and of Department PNAS NSlicense.y PNAS | uy9 2019 9, July | o.116 vol. b,1 A | and o 28 no. 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APPLIED PHYSICAL SEE COMMENTARY SCIENCES ABCDDaguerreotype process 14 Hg1-UG 7 (i) (v) 0 Ag Hg 14 Hg4-UG 7 (ii) (vi) 0 2- 14 Hg1-G I2/Br2 S2O3 7 Particle count 0 h (iii) (vii) 14 Hg4-G Au 7 0 150 300 450 600 750 (iv) (viii) Particle size (nm)

Fig. 1. Daguerreotype characteristics. (A) Daguerreotype in the study collection of The Metropolitan Museum of Art (artist unknown, ca. 1850s). The perimeter has a gradient created by an oval mask applied during sensitizing and development. (B) Scanning (SEM) images, outlined in colors corresponding to colored circles in A, show varying nanoparticle densities, from Top to Bottom, in highlight, midtone, shadow, and blue-tinted regions of the image. (Scale bars, 2 µm.) (C, i–viii) Schematic outlining the steps of the daguerreotype process. (D) Particle size counts, averages ( dashed line), and SD ( bar) for daguerreotype samples (Insets). Hg1 and Hg4 refer to minutes of mercury , and UG and G refer to ungilded and gilded plates, respectively. Blue lines represent blue mask regions, while gray lines correspond to the regions of highest light exposure (i.e., highest particle density) of the exposure step wheels, marked by gray circles in Insets.

and compared with the number of daguerreotypes reported (Fig. 1 C, iii). With ever-changing parameters like to have been produced in the , only a relatively affecting their protocols, daguerreotypists relied on the observa- small number of plates have been examined beyond conven- tion of the color arising from reflection on the silver layer tional optical microscopy with spectroscopic techniques, scan- to estimate the readiness of the plate (48, 52). As the process ning electron microscopy (SEM), and other nanoscale improved, the ideal layer color evolved: Daguerre’s first recom- methods capable of examining and characterizing the nanos- mendation was golden , with an average film thickness of tructures on their surface (6, 36–47). Unfortunately, time and 30 nm (52), but later changed it to “-,” the color known exposure to the elements have irreversibly altered 19th-century after 1859 as (48, 53). After 1840, further sensitization daguerreotype images, making it difficult to use them to char- with bromides and chlorides followed, the additional halides cre- acterize their properties. Also, it is rarely possible to remove ating trap states in the crystalline film that broadened its spectral microsamples for analysis from these unique objects. In this sensitivity across the visible , thereby shortening light context, creating model daguerreotypes strictly following 19th- exposure times by up to a factor of 60. Exposure to light (Fig. 1 C, century practices becomes necessary, especially to recreate iv) catalyzed a photolytic reduction of the silver halides to create certain visual effects that have been observed in historical the (Fig. 1 C, v), metallic silver clusters with diame- plates (42–44, 48). ters likely no more than 1–2 nm (54), which serve as nucleation In this article, we attempt to shine light on the daguerreotype’s sites for crystal growth by development with mercury (Hg) vapor. dimensionality using a unique combination of daguerreotype Mercury development took only a few minutes and resulted in artistry and expertise, experimental nanoscale surface analysis, fast formation of silver–mercury nanoparticles (Fig. 1 C, vi), via a and electromagnetic simulations, to uncover the plasmonic prop- complex combination of oxidation–reduction reactions, electro- erties of these early photographs. This combination provides a static processes, mass transfer of silver and mercury, and Ostwald unique into the mechanisms that give rise to their ripening of metallic clusters (48, 55, 56). Afterward, the plate optical response, thus serving to inform the development of was placed in a bath of aqueous thiosulphate (Fig. 1 C, vii) to preservation protocols, as well as novel approaches to future dissolve the unexposed silver halides and stop the light-sensitive technologies inspired by past ones. reaction, a process known as “fixing.” In a last step commonly referred to as “gilding,” a salt solution was poured over Results and Discussion the mercury-developed image and heated with a lamp. This cre- Soon after Daguerre’s first manual was published, the daguerreo- ated a nanoscale layer of gold (Au) on the surface, improving type process rapidly spread across England and North America the visual and, in principle, producing a more stable (6, 48). Each of the numerous steps to make a daguerreotype image (43, 44, 57). demanded parametric control that strongly affected the appear- The macroscale result is a unique and irreproducible posi- ance of the final image, of which a lack of mastery contributed tive image encoded in the nanoscale by metallic nanoparticles to the failure of many early attempts (49–51). For a process that of myriad sizes, compositions, and surface densities. The Ag-Hg was as much a protocol as it was an art, diagnosing problems and particle sizes are correlated with the density of latent image sites, obtaining desired results were accomplished by experimentation. which depends on the amount of light exposure on that area, The steps involved in making a daguerreotype are summarized as the concentration of mercury during development should in Fig. 1 C (for detailed information, see Materials and Methods). remain relatively uniform across the exposure field (48). Thus, First, a silver (Ag) layer was joined to a plate by cladding areas with lower nanoparticle density tend to have larger, more and, in some instances, an additional layer of silver was deposited mercury-rich particles spaced farther apart, while high-density by (termed “galvanizing” in the 19th century) areas have smaller, silver-rich nanoparticles (6, 36, 41–43, 45, 48). (Fig. 1 C, i and ii). The silver surface was polished and then sensi- The daguerreotype’s optical response results from the collective tized with fumes to create a photoactive silver iodine layer light scattering produced by the ensemble of nanoparticles.

13792 | www.pnas.org/cgi/doi/10.1073/pnas.1904331116 Schlather et al. Downloaded by guest on September 27, 2021 Downloaded by guest on September 27, 2021 h vrg iesoso h oaie ein fteHg1-UG to the of corresponding regions sizes solarized with the of particles dimensions for average calculated the 3A, Fig. in blue a the from one. evolve increases, red end to a angle expected red to is viewing the daguerreotype the on the as of mode color large Therefore, the at spectrum. by while, the dominated be blue/UV, of is to the response response in its the located expect angles, mode we small the vertical, by at the dominated to observed respect the when with of angles these Specifically, dependence of angle response. patterns the radiation on daguerreotype consequences the in direct in has shown difference modes the large pattern to The doughnut-shaped respect 2G. with the Fig. angles with high 2E, direction, at Fig. radiates vertical in one seen second as direction, the vertical while the 2 in Fig. mostly radiates in mode the shown by plots confirmed as charge substrate, the to oscillate (≈670 perpendicularly that spectrum and dipoles (≈365 parallel with the respectively, spectrum of associated, are part the narrow modes red two of a the is in part modes: incidence one different blue/UV broader of two the angle by in the dominated peak is cases, black spectrum the all The while In 2B), with light. illumination (Fig. representing unpolarized light average, their polarized to P corresponds line or illu- for S results with the respectively, mination indicate, curves solv- ( red and by equations blue calculated The Maxwell’s sample, solarized numerically Hg4-UG ing the from size cle ueet 4,4) hl h usrt a sue ob pure be to d assumed was 2C substrate with Fig. the silver. accordance while in 48), (47, mea- alloy, surements (SEM-EDS) mercury was nanoparticle dispersive silver–30% energy the 70% SEM-coupled of a material The as 2B. taken Fig. in schematics dimensions the with ellipsoid symmetric axially d an 2A). as (Fig. it from (HA-SEM) modeled obtained We microscopy information electron on scanning individ- based high-angle surface, representative chosen a its nanostructure of on response ual nanoparticles optical the the by investigated we determined are image type gilding size and final diameter the particle average from distribution. the overall layer the from increases Au deviations also size The step larger diameter. as over- particle well larger average to as lead diameters, times particle and 1D, development all Fig. diameter Hg in longer shown (UG) particle that (AFM), the ungilded of confirms microscopy and force as Analysis atomic (Hg4), to using respectively. min height referred (G), 4 gilding, gilded or of (Hg1) or presence min develop- or 1 Hg the either absence wheel: being step the time, of ment tone and samples, blue appearance these of the shade bor- In and varying incidence. the outer determine normal wheel solarized conditions experimental at a step two blue and exposure appears highlights an which to der, 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blue/UV the the direction: in vertical located the entirely to respect dif- 30 with four angles at samples, viewing curves) ferent (dashed Hg4-UG and curves) (solid respectively. nm, 670 and nm 365 at calculated ( modes, results. ( averaged polarization to P and corresponds or S curve with black illumination the for results the respectively, diagram Schematic (B) with ( nm.) tructure geometry. 200 simulation bar, the (Scale of surface. daguerreotype the nanostructures of on image (HA-SEM) microscope electron scanning High-angle 2. Fig. DF C A EG 0 5 0 5 900 750 600 450 300 ◦ Scattering intensity , F n aito atr (E pattern radiation and ) 60 nlsso h pia epneo nidvda aotutr.(A) nanostructure. individual an of response optical the of Analysis Horizontal dipole ◦ and , =365nm h = 80 8n and nm 98 ◦ sepce,for expected, As . 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APPLIED PHYSICAL SEE COMMENTARY SCIENCES ABCEDFG Scattering intensity Scattering intensity

300 600 900 Hg1-UG Hg4-UG 300 600 900 Hg1-G Hg4-G Wavelength (nm) Wavelength (nm) H I Au/Ag shell h h Ag/Hg Ag/Hg particle core d d

Ag substrate J K Au/Ag substrate

Fig. 3. Viewing angle dependence of the daguerreotype image. (A) Calculated scattering intensities for 0◦, 30◦, 60◦, and 80◦ viewing angles for the Hg1-UG (solid curves) and Hg4-UG (dashed curves) samples. (B and C) Microscope images of the surface of the Hg1-UG and Hg4-UG samples taken at the angles shown in A. (D–F) Same as A–C, but for gilded samples. (G) Photographs of the entire Hg1/4-G sample taken at different angles. The left part of the plate corresponds to the Hg1-G sample, while the Hg4-G sample is located on the right. (H and I) HA-SEM images of the structures in model ungilded and gilded daguerreotype samples, respectively. (Scale bars, 500 nm.) The schematics at Left of the SEM images describe the geometry used to model the response of the nanostructures. (J) Baalbec, 1844. Petit et Grand Temple, Girault de Prangey, Bibliotheque` Nationale de (ark:/12148/btv1b6903484v). Source: gallica.bnf.fr/National Library of France. (K) Ramesseum, Thebes, 1844. Girault de Prangey, The Metropolitan Museum of Art (2016.604).

dependence results from the different nature of the modes sup- and broader peaks, as well as an overall , compared with ported by the nanoparticles, their wavelengths, as well as the the Hg1-UG sample. scattering intensity, depend on the actual size of the nanoparti- The variation of color hue with viewing angle also occurs cle. Indeed, examining Fig. 3 A–C, we observe that the Hg4-UG for gilded daguerreotypes, as shown in Fig. 3 D–F. These sam- sample, which has larger average particle sizes, displays larger ples, as discussed above, underwent an extra step in which a

13794 | www.pnas.org/cgi/doi/10.1073/pnas.1904331116 Schlather et al. 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S. Albrektsen, O. Pors, A. Roberts, S. A. 19. colors. structural of Physics Miyazaki, J. Yoshioka, S. Kinoshita, S. 15. a on based filter Color Lee, D. K. Kim, H. S. Lee, S. S. Yoon, T. Y. Lee, S. H. 11. 2 .C real,D .Pzo .Mnes .A zn htnccytlfull-colour colour Photonic-crystal high-resolution Inoue for D. nanoresonators Ozin, Plasmonic 14. Guo, J. A. L. G. Luo, X. Manners, Wu, K. Y. I. Xu, T. Puzzo, 13. P. D. Arsenault, C. A. 12. Taft, R. 10. clte tal. et Schlather eete acltdb nertn h nue nryflxoe surface, a over flux intensities energy induced Scattering the boundaries. integrating by outer calculated then the were perfectly from stopping absorbers, using reflections near-perfect truncated as was nonphysical act calculate These size to domains. domain input (PML) as The layer step system. matched previous the the of in The response obtained domain. the fields extending the incidence infinitely used an an step simulate next to had used which were boundaries wave, odic plane 45 monochromatic of a angle extend- for infinitely an substrate from optical fields First, ing transmitted the approach. and two-step reflected calculated the a computed We using the we system of (64). particle–substrate function the theory for dielectric medium using response data The effective mercury mercury. ref. and Bruggeman silver for from the the alloy, 63 from gold–silver constructed ref. the was from alloy for silver–mercury and 61 silver, ref. for from data. tabulated of data 62 from functions used taken we thicknesses dielectric were particular, models the The the In than samples. in smaller used experimental materials much field the different is electric the of range the substrates visible of the the distance This in of penetration ones. silver gilded the and the that gold for fact silver in 10% the and by gold justified 90% sys- with ungilded was substrate the alloy for an the silver of pure cases, and of made tems all space semiinfinite In a nm). as modeled the was of we (≈30 and dimensions 3, samples gold averaged 90% the experimental Fig. match with to corresponding of alloy chosen an schematics thickness of a 30% made the with particle silver, and in 10% the silver to shown 70% shell as conformal of a systems, mixture added gilded a as the modeled For was mercury. particles the specified, the of otherwise of types unless former, different material the two For analyzed ungilded. we and work, gilded this systems: Throughout as 2B. labeled Fig. dimensions in primary shown two the with ellipsoids symmetric .L .M Daguerre, M. 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Kristensen, Kristensen A. A. Mortensen, A. 31. N. Højlund-Nielsen, E. Vannahme, C. Zhu, X. 30. display. color dynamic for materials plasmonic Advanced Wang, J. Zhuo, X. Shao, L. 26. eshlGf,Jsp uizrBqet 06Bnfi ud n itof Gift and F. Joyce Fund, (2016.604). Moran, Benefit 2016 Family, Chisholm 2016 and Louise Sackler, Bequest, Theresa of and Sackler, D. Mr. Pulitzer memory Mortimer Dr. Purchase, in Joseph Art. Gift, Gift, of Moran Menschel Museum A. Metropolitan John The Mrs. this Met– Prangey, of the de support in generous Girault credits: their staff for the Photography Departments and Education project. Center the Research and PC, Science University DSR, City Advanced the York and as well New (PC); as of Conservation Photographs; Scien- of Department of We Kennedy, Pinson, Department Met). W. C. Annette Leona, Stephen (The Nora Marco an Art (DSR); colleagues of Research by Met in Museum our tific supported to Metropolitan Assistance grateful was The also at Graduate A.E.S. are Fellowship the fellowship. Renta la and Need program de National Fellowship Microsystems of Family and acknowledges Areas P.G. Nanoscience Whitten work. UNM the Com- this the through Research in from Advanced used support for resources financial Center computational (UNM) for Mexico acknowledge New puting also We of ECCS-1710697). University (Grant the Foundation for Science checked National were work ACKNOWLEDGMENTS. the size. in domain presented and compu- mesh results to the the respect reduce with of to convergence these symmetry All of used polarized cost. results we P the tational possible, averaging and by When S obtained simulations. both were unpolarized two spectra for for final response separately the the done and simulate light, were To wave- nm. calculations of range these 900 the to light, over nm swept 300 then from was lengths simulation two-step 7.5 a This in interest. boundary, nanoparti- scattered semispherical light the a only of used collected we surface which scattering, the angle-dependent was the For integration total cle. For of scattering. boundary angle-dependent the or total scattering, either for selected was which nue leain ndgeroyeiaeprils ihrslto SEM-EDS resolution high A particles: image daguerreotype study. in alterations induced by Daguerreotypes (2010). spectrometry. century 654–661 21st fluorescence of X-ray restoration wavelength-dispersive and degradation process, tographic 99–109. pp Mexico), ypsu nAcaooia n rsIse nMtra cec LSA IMRC & (LASMAC Vel Science A. 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13798 | www.pnas.org/cgi/doi/10.1073/pnas.1904331116 Schlather et al. Downloaded by guest on September 27, 2021