Surface Science 500 (2002) 10051023 www.elsevier.

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The surface science of xerography

Charles B. Duke a,*, Jaan Noolandi b, Tracy Thieret c
a c

Xerox Corporation, Wilson Center for Research and Technology, 800 Phillips Road 114-38D, Webster, NY 14580, USA b Xerox Corporation, Xerox Research Center Canada, 2660 Speakman Drive, Mississauga, Ont., Canada L5K 2L1 Xerox Corporation, Wilson Center for Research and Technology, 800 Phillips Road 114-41D, Webster, NY 14580, USA Received 22 May 2000; accepted for publication 19 April 2001

Abstract Over the past four decades xerography, the dry ink marking process developed by the photocopy industry, has grown from nothing into a $170 billion industry worldwide. This amazing commercial success is due to the fact that during this period, xerographic technology experienced constant and often-dramatic improvement created by sustained industrywide research and development. Indeed, the development of the xerographic copying and printing industry is one of the great applied surface science successes of all time. In this article we outline the story of the advances in xerographic technology during the past four decades, describe the profound dependence on these advances of the control of surface and interface properties of increasingly sophisticated multi-component materials systems, and indicate the potential impact on the industry of the continuing development of the surface and interface science of the multi-component materials packages used in xerographic technology. 2001 Elsevier Science B.V. All rights reserved.
Keywords: Adhesion; Dielectric phenomena; Electrical transport (conductivity, resistivity, mobility, etc.); Photoconductivity; Surface electronic phenomena (work function, surface potential, surface states, etc.); Surface energy; Surface melting

1. Introduction The practice of xerography began in 1938 with Chester Carlsons rst xerographic print [1,2]. That humble beginning in an apartment in New York City spawned the biggest change in work practices in the history of the oce. The rst demonstration of the system contained the essential elements of the modern electrophotographic copier or printer. The xerographic process consists of creating an electrostatic image on a photocon-

Corresponding author. Tel.: +1-716-4222106; fax: +1-7162655080. E-mail address: cduke@crt.xerox.com (C.B. Duke).

ducting drum or belt, developing that image with a pigmented charged powder called toner, transferring that image to a substrate, typically paper, and then melting the toner to fuse it onto the substrate. When in 1959 this process was embedded into the legendary 914 copier, the world changed forever. Hand copying and carbon paper were banished; access to personal information was democratized; and the era of personal publishing began. Most readers of this article have never known a world without the convenience of personal copying and printing. 1959 marked the dawn of the modern information era. From these modest beginnings, printing and copying using the xerographic process is an industry that has been generated by over four decades

0039-6028/01/$ - see front matter 2001 Elsevier Science B.V. All rights reserved. PII: S 0 0 3 9 - 6 0 2 8 ( 0 1 ) 0 1 5 2 7 - 8

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of continual improvement of the implementation of the xerographic process steps. Many of the improvements are the result of sophisticated materials packages whose design and operation rely heavily on the understanding and control of surface and interface properties. Thus, xerography is a technology that has been generated and advanced by the control and utilization of interfacial phenomena. The story of the development of the xerographic copier/printer industry as a case history in value of basic research in US industry has been summarized by the Committee for Economic Development [3]. In this article we describe the xerographic process, indicate some of the major material challenges in designing a modern, commercial xerographic marking engine, and develop several illustrative examples of the role of surface and interface science in overcoming these challenges. This might be a footnote in history of minor interest to the intended audience for this volume, rst year graduate students in a wide variety of scientic and engineering disciplines, but for one thing: During the past decade the world has changed profoundly and with it the practice of both science and engineering. The world has entered an era of unprecedented pace in the generation of new knowledge and its commercial application in global markets. The search for new knowledge is increasingly pursued in a context in which its application to generate economic value is valued even more highly than the novelty and impact of the knowledge itself. Few of todays rst year graduate students will pursue their careers without repeatedly feeling the need to solve practical problems under tight time constraints. The story of the development of xerographic technology by solving dicult, practical surface science problems is a harbinger of the future. By appreciating the whys and hows of the development of xerography, you set forth the elements of a blueprint for your own professional success in this new world.

2. Industry overview Xerographic printing and copying is big business. The scope of the industry is monitored by

several consulting rms, one of which is CAP ventures from whose services we take the data noted below [4]. From the humble beginnings of Chester Carlsons kitchen experiments in 1938 and the rst automatic copier in 1959, the worldwide market served by xerographic marking engines and the services built around them has exploded to become $167 B in 1998 growing at 12% per year. This corresponds to 1.2 trillion pages made by xerographic printers, copiers and fax machines. For comparison, the corresponding number of pages made on desktop ink jet marking engines is 160 billion, i.e., nearly 10 times smaller. As indicated in Ref. [3], this entire industry and its amazing growth is an outcome of an aggressive research and development (R&D) program carried out over six decades. Much of this R&D was devoted to solving surface and interface technical problems needed to produce better image quality, improved reliability and lower cost of xerographic products. An important aspect of the industry is that its business model derives an important portion of its prots from selling consumables, specically the dry ink and replacements for some of the parts that wear out over the life of the engine (like tires on an automobile). Dry ink is the black powder that you get all over you when it is not adequately fused to the paper or when you try to change the bottle of dry ink and spill some. In 1998 the dry ink market alone was over $8 B growing at 10% per year, and shared by over 12 multi-national rms, with the largest shares being held by Xerox and Canon. One of the important replacement parts is the photoreceptor, the worldwide market for which in 1998 was approximately $10 B. As we see below, both photoreceptors and the dry ink are complex, multi-component organic composites designed and tested using sophisticated surface science concepts and instrumentation. Thus, through the vehicle of xerographic consumables, surface and interface science and technology are exerting a decisive inuence on over $20 B of cash ow every year: a number that is comparable to the entire US annual expenditure for basic research in recent years [5].

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3. The xerographic process: description of process steps As indicated above, the xerographic process consists of ve process steps that begin by charging a photoconductive belt or drum; generating a latent image on this photoconductor by imagewise exposure to light; development of this latent image with charged toner; transfer of the toner image to a substrate; and fusing of the image to that substrate. A sixth process step, the cleaning of residual charge o the photoreceptor, is needed in commercial devices to reuse the same photoreceptor for subsequent imaging. We begin this section with an explanation of the nature and operation of the subsystems that together comprise a monochrome xerographic marking engine, as illustrated in Fig. 1 [1,2,610]. 3.1. Photoreceptor The photoreceptor is the central element of the xerographic process. This devices fundamental responsibility is the transport of the page images of a document in their various forms through the steps of the process. While performing this function the photoreceptor also serves as the imagegenerating surface. Specically, charge deposited on the photoreceptor is discharged imagewise by the photogeneration in a charge-generator layer of holes that migrate to the negatively charged upper surface to discharge this surface as shown in Fig. 2 [1,2]. The device is a loop that recycles through the process steps. It may be realized either as a rigid drum or as a belt, as shown in Fig. 1. A detailed description of the operation of multi-layer photoreceptors is given in Refs. [2,6]. Designing and fabricating a multi-layer photoreceptor that is stable for hundreds of thousands of impressions and supports resolutions of up to 1200 spots per inch uniformly across its page-size surface is a challenging technical problem which involves the solution of multiple interface science problems as indicated in the caption to Fig. 2. For contributions to this feat for the belt photoreceptors used in the Xerox 10 series and subsequent products Damodar Pai, Jack Yanus, and Milan Stolka of

Fig. 1. Schematic diagram of the monochrome xerographic process. A photoreceptor belt is uniformly charged in step (1). An image is written on this belt by a laser in step (2), thereby generating a charge image on the belt. This charge image is converted into a powder image of toner on the belt in the development step (3). This powder image is transferred to a sheet of paper in the transfer step (4) and subsequently fused to the paper in step (5). Residual toner on the photoreceptor is cleaned o in step (6) and the process repeats.

Xerox received the Heroes of Chemistry 2000 award sponsored by the Industry Relations Oce of the American Chemical Society. This illustrates a rst lesson for prospective surface scientists: Outstanding applied surface science is recognized not only by ones sponsors, but also by ones peers. 3.2. Charging In most xerographic architectures the charging subsystem is presented with a clean (of toner) and erased (of static electric charge) photoreceptor as indicated in Fig. 3 [1]. Its output is a uniformly charged photoreceptor surface at a dened voltage. The charging device is typically a ne tungsten wire operated at a few hundred volts DC and a few thousand volts AC. This current produces an ionization of the air in its vicinity. These ions are the source of a corona wind that charges the photoreceptor. A corotron-charging device is built by surrounding the wire with a grounded aluminum housing on three sides [1]. In modern charging

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Fig. 2. Successive blow-up diagrams of the structure and operation of a multi-layer photoreceptor belt. The multiple interface, photogenerator and transport layers are coated on a polyethylene terephthalate (PET) belt. The operation of the photoreceptor in a xerographic marking engine is shown in the diagram in the left-hand panel. The physical processes that occur to discharge the photoreceptor upon exposure to light are indicated in the diagram in the lower right-hand corner. The light penetrates through the charge transport layer and is absorbed in the charge generation layer where it generates an electronhole pair. The hole migrates to the front of the photoreceptor where it discharges the charge pattern on the surface. The electron migrates to the grounded electrode and ows to ground. Designing multi-layer photoreceptors involves the solution of sophisticated interface science problems associated with charge injection across the various interfaces, assuring that charge does not get trapped either in the layers of the photoreceptor or their interfaces, and guaranteeing that charge does not spread as it is generated and transported across photoreceptor so that resolutions of up to 1200 dpi may be achieved uniformly over page-size images.

devices, called scorotrons, a biased mesh grid is interposed between the wire and the photoreceptor [1]. This grid enforces a charge limit. As the device charges toward the grid potential, the electric eld between the grid and the photoreceptor surface drops to zero, leading to a known uniform voltage at the exit from the charging station. This is a good example of the use of passive elements operated using physical principles to stabilize the xerographic process. 3.3. Exposure/illuminator The exposure station receives a photoreceptor with a uniform charge spread two dimensionally across its surface. In modern digital xerographic marking engines the photoreceptor is discharged

imagewise by a laser beam so that the output is a latent image in which the charged and discharged areas of the photoreceptor are a reection of the image that ultimately appears on the output medium. Such a station is indicated schematically in Fig. 4 [1,2]. Usually the discharged areas correspond to the black areas in a monochrome image. Gray areas are described by halftone dot patterns [11]. Typical resolutions are 6001200 dots per inch (dpi). The desired imaging property of the photoreceptor is that in the dark, the device functions as a capacitor, maintaining an electrostatic voltage between the upper surface and the ground plane on the lower surface. When exposed to light, however, the device becomes a conductor. The voltage drops to near zero. Because there is little lateral

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Fig. 3. Schematic diagram of a corotron charging subsystem. A corotron wire at high voltage generates negative ions that ow onto the photoreceptor belt to give it a uniform charge as it passes below an orice in the grounded shield surrounding the wire. Sometime a grid is added below the orice to better control the potential on the photoreceptor. In this case the charging subsystem is called a scorotron. In recent years completely solid-state versions of these devices have been built and tested, but have seen limited deployment in the industry. The perfection of such charging bars remains a challenge for the next generation.

Fig. 4. Schematic diagram of the exposure (illuminator) subsystem. A laser beam is swept across the surface of the photoreceptor by a rotating polygon of mirrors. The beam is turned on and o imagewise either by a modulator or by the current through a laser diode. Everywhere that the beam strikes the photoreceptor, it is discharged as indicated by the absence of a charge pattern. Many technical challenges face the designer of a commercially successful diode-laser-based illuminator including selecting a combination of laser life, laser power, laser spot size, laser pulse shape, photoconductor sensitivity, optical and polygon design that satisfy the cost, stability and compactness requirements of a modern xerographic marking engine.

conduction, a small spot of light produces a localized area of voltage dierence. These properties

are achieved by the multi-layer photoreceptor architecture indicated in Fig. 2. Residual, trapped charges prohibit the exposed voltage from achieving the ground potential. Aging of the photoreceptor includes increases in both the dark decay, where the device voltage decreases with time even in the dark, and the residual potential, the minimum voltage achievable upon exposure. Reducing aging and dark decay to allowable limits is a challenging problem involving considerable use of surface science techniques and tools to identify and mitigate the root causes of these phenomena. A modulated or diode laser provides a convenient source of light to expose the photoreceptor in an imagewise way. The light is scanned laterally using a polygon mirror rotated at a constant angular velocity. The photoreceptor motion provides the second dimension linear variation so that a raster scan is produced on the photoreceptor surface much in the same way that a television picture is generated. The resolution is typically limited by practical design considerations (e.g., laser power, photoreceptor sensitivity, cost of the optics) rather than fundamental physical phenomena (e.g., charge spreading on the surface of the photoreceptor). More detailed descriptions of the illuminator subsystem that exposes the photoreceptor may be found in Refs. [1,2]. The design and fabrication of the diode lasers for use in illuminators is a challenging technical problem in its own right. Don Scifres, Robert Burhnam and William Streifer developed the pioneering technology for one of the early generations of semiconductor diode lasers at the Xerox Palo Alto Research Center (PARC). Scifres spun out the design and manufacturing technology from PARC as the rm SDL to manufacture these lasers for Xerox. Subsequently SDL has become a major supplier of lasers to the entire optical communications industry, and Scifres has remained its chief executive ocer (CEO). Scifres and Burnham were elected to the US National Academy of Engineering for their contributions to this technology. Scifres also was awarded the 1997 George E. Pake Prize of the American Physical Society for his role in commercializing the technology and thereby generating jobs for young scientists and engineers. This illustrates a second lesson for prospective

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surface scientists: Such are the rewards awaiting successful young scientists and engineers in the new world of global commerce. 3.4. Registration In color-printing systems the photoreceptor must be imaged separately for each of four (cyan, magenta, yellow and black or CMYK) color separations. One way to do this, the multi-pass cyclic architecture, is shown in Fig. 5. The four color panels must be registered relative to one another. Mis-registration results in undesirable color shifts, image blur, unimaged areas, and other defects. The timing of the individual exposure steps is regulated such that the images overlay one another within a few 10s of microns. In the colorprinting architecture shown in Fig. 5, there is an additional registration requirement. When the individual color separations are built up on the output media, these transfer steps must occur with the same level of precision. A description of the various architectures used to implement color xerography may be found in Refs. [1,6]. The solution of the color registration problems is an active area of research in modern control system design. The use of novel sensors on the photoreceptor and

feedback loops to the motion control of the photoreceptor or the illuminator is enhancing the precision of the registration from the order of 80 100 lm to the order of 10 lm, at which point the human eye can no longer detect mis-registration defects. The integration of these sensors into the photoreceptor involves the solution of a host of surface and interface problems new to the practice of xerography, thereby generating challenges for the next generation of xerographers. 3.5. Development The development subsystem is presented with a latent image on the photoreceptor. Upon exit the toned image is visible on its surface. A schematic diagram of a magnetic brush development subsystem is shown in panel (a) of Fig. 6 [1,6], although many other types of subsystems are used commercially [1,6]. Within the magnetic brush development subsystem there are two major materials components collectively called developer and illustrated in panel (b) of Fig. 6. The rst is the toner, or dry ink. Toners are complex multi-component composite materials packages the composition of which is indicated in panel (c) of Fig. 6. Toner is the most challenging materials package in the system

Fig. 5. Schematic diagram of the cyclic color xerographic process. In this process one color is imaged, developed and transferred in each pass of the photoreceptor belt. The developers for the other colors are cammed out as indicated by the arrows in the diagram. The four-color image is built up on the paper as each of the four developed powder images is transferred sequentially. Then, the nal fourcolor image is fused as it exits the transfer zone.

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Fig. 6. Successive blow-ups of a development subsystem (panel (a)), development zone and carrier bead (panel (b)), and toner particle (panel (c)). Key parameters and features of each of these are indicated in the gure.

because there are so many properties it must exhibit. These include powder and viscous ow, charging, melting properties, color, toxicity, size, and adhesion to the various surfaces with which it comes in contact during the xerographic process.

Many of these properties deal with how the toner interacts with surfaces. Powder ow governs the capability of the toner to be dispensed from the hopper to the developer housing and once there, to mix well with the contents. Additives are required

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to generate suitable performance. Viscous ow determines the ability of the toner to wet the surface of the output medium when melted by the fusing subsystem. Melt properties are constrained by a desire to reduce the temperature required to fuse the toner to the output media, and hence energy consumption, on the one hand, and on the other hand by requirements for storage in hot environments. There are stories of toner bottles turning into big crayon containers after transport in trucks across the desert because their blocking temperatures (i.e., the temperature at which the toner spontaneously aggregates in the bottle) were too low. Size distribution is a determinant in image quality. Large toners make sharp edges in images look blurry. Small toners are dicult to contain and can become airborne contaminants. Pigments may not be chosen arbitrarily. They must pass toxicity testing and also must produce the desired colors. The loading of the pigments into the toner polymer base (see panel (c) of Fig. 6) must not be excessive or the pigment will dominate the other properties. Release properties come into play when, during fusing, the toner must adhere to the output media rather than to the fuser roll (see Fig. 8) to be deposited on a subsequent sheet in a process called hot oset. With all these constraints, the challenge of constructing a material that satises them is quite a challenge. The design and fabrication of the sophisticated multi-component toner materials packages are discussed in Ref. [8]. They remain one of the major challenges for surface scientists in xerography. As shown in panel (b) of Fig. 6, there is commonly a second component in the developer housing. The carrier is typically a ferrite of about 100 lm diameter. These carriers form brushes which are rotated by the magnetic elds in the developer roll as indicated in panels (a) and (b) of Fig. 6. The toner, when agitated against the carrier, develops a triboelectric charge and adheres to it. Typically this requires the ferrite core of the carrier to be coated with an organic polymer that yields the desired charge exchange. Together this mixture is referred to as developer. Developer aging occurs when the toners impact the surfaces of the carrier particles, diminishing the carrier surface area available for tribocharging. One of the

responsibilities of the development system is to use the electric eld generated by the photoreceptor image charge to inuence the charged toners to migrate to the photoreceptor. Thus, the two forces holding the toner to the carrier must be overcome. Both electrostatic forces and the adhesion forces are commonly broken by agitation of the developer in or near the nip created by the development roll and the photoreceptor surface. A bias is applied to the housing to generate the electric elds for development. The value of this bias voltage lies between the photoreceptor voltages for the charged and discharged areas. Thus, a potential is generated in the nip that produces a force, the product of the toner charge and the external eld that for the toned regions points toward the photoreceptor. The same bias produces a similar force in the untoned regions of the image but in the opposite direction, thereby driving the toners away from the photoreceptor toward the developer roll. The development subsystem described in Figs. 1 and 5 is called discharged area development in which the negatively charged toners migrate toward the uncharged (i.e. exposed) areas of the photoreceptor [1,2]. Unlike lightlens copiers, in which the charged areas are developed, this is the common mode of exposure for digital printers and copiers, selected primarily in order to extend the life of the laser by reducing its duty cycle. As is the case for the other subsystems, the design of new developer subsystems is an active area of research. The essential physics problem to be solved is to insure the reliable transport of toner from the bottle that you insert into your copier or printer onto the photoreceptor at precisely the right place for hundreds of thousands of copies completely uniform across the page. One might think of this as applied soft condensed matter physics. In the early 1980s a new system design called highly agitated zone (HAZE) development was invented which provided both excellent broad area and image detail development with hardware that was smaller and lower cost than its predecessors. This design was rst incorporated in a 62-copies-per-minute Xerox product, the Xerox 1065 Marathon copier, introduced in 1987. Over the past 13 years, this product family has produced

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more than 100 000 machines in the US. Furthermore, the HAZE design was subsequently incorporated in several additional major Xerox product platforms for copiers and printers. The combined revenue from all of the products embodying this development system was nearly half of Xerox total revenue in 1996. In recognition of the contribution of the HAZE development process to the success of three generations of Xerox current products, the inventor of the process, Dan Hays of the Xerox Wilson Center for Research and Technology, was awarded the 1997 American Institute of Physics Prize for Industrial Applications of Physics. More innovations like this are in the pipeline, especially with the decreasing size of marking engines and the move to color. Lots of surface and interface problems must be solved to move little 5 lm toner particles around over 10 in. swaths, so there is ample opportunity for surface and interface scientists in this area. This illustrates a third lesson for prospective surface scientists: Opportunity abounds, and fame as well as fortune awaits those who generate important new inventions. 3.6. Transfer The transfer step begins with a toned photoreceptor image and a sheet of media. The toner is transferred from the photoreceptor to the media with a minimum of residual mass remaining on the photoreceptor as indicated in Fig. 7. This process uses electrostatic forces on the toner charge to encourage it to move to the paper. Corotrons or biased rolls are used to manipulate the toners electrostatically. When printing color in the normal way by mixing together a set of primaries, variations in the transfer eciency alter the amount of transferred toner from each constituent and result in noticeable dierences in color reproduction. Transfer eciencies in excess of 98% are typically achieved in modern xerographic marking engines, but even at this gure ecient, stable transfer remains one of the major research problems limiting the performance of modern xerographic marking engines. This is a promising area for a prospective surface scientist to establish her or his fame and fortune.

Fig. 7. Schematic diagram of a transfer subsystem. A corotron biases the incoming paper positively so that it attracts the negatively charged toner to transfer from the photoreceptor. The geometries shown in this gure are highly idealized.

3.7. Media handling In order to position the media to receive the xerographic image at the transfer station, additional processes must be considered. Sheets of paper (or vugraphs) must be removed from a stack, transported to the transfer station, and presented to it at the precise time such that the arrival of the photoreceptor image and the media may be synchronized within an accuracy of a few tenths of millimeters. The most common type of media is cut sheets, although the use of continuous webs is sometimes employed in high-throughput printing systems. The properties of media vary greatly from one type to another and sometimes even from sheet to sheet (e.g., the use of dierent weights and nishes of paper in a single document). In some printing systems the media are escorted through the system with gripper bars or tacked to an electrostatically charged transport medium. In most electrophotographic systems, however, the media are passed between subsystems and, after marking, sent to the nishing station, by mechanical devices that rely on frictional forces. The development of gentle media handling systems based on distributed sensors and actuators is a major frontier of modern printing systems research, due to the high importance of handling a wide range of media in color printing. This is a huge opportunity for the development and application of unique microelectromechanical (MEMS) devices and technology to the printing business by the next generation of applied physicists.

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3.8. Fusing Most readers of this paper are probably aware of the fuser in their xerographic copier or printer because documents in the output tray are warm to the touch. Simply put, the fuser takes the toner powder transferred to the paper by the transfer subsystem and xes it to the paper by melting it, usually by applying heat and pressure, so that it ows into the bers of typical oce paper or into a specially prepared surface layer on coated stock or transparencies. Once the toner is on the media as it exits the transfer subsystem prior to fusing, it may be readily smudged (or even blown o) because the only forces holding it are the electrostatic forces remaining from the transfer step. Fusing melts the layers of toner on the media to achieve xing the image as indicated in Fig. 8 [8,9]. The heating may take place using a radiant source or more commonly a heated roll, which assists the xing of the toner to the media by pushing it into the media. These rolls are sometimes coated with a functional oil (called a release agent) that forms covalent bonds with the roll surface in order to keep the toner from adhering to it. Roll fusers are complicated multi-component materials systems, embodying multiple layers of composite materials.

Their design and fabrication are discussed in Refs. [9,10]. When an electrophotographic printer/copier is rst turned on, the warm up time is consumed in heating the fuser. Indeed, during warm-up, all the power available to the device is used to heat the fuser as rapidly as possible. As xerographic devices become faster, image quality requirements become higher, and power constraints become tighter, research is moving toward belt fusers, that can warm up much faster and use a lot less power than roll fusers. This is an arena ripe with opportunity for the applied surface scientist and the control engineer to collaborate on designing smart fusers and associated toners that precisely fuse the images on each sheet, at minimal power, image by image, without a smudge or smear to be seen. 3.9. Cleaning and erase The photoreceptor cycle is completed in the cleaning and erase stations. Input to these subsystems is a surface that has untransferred residual toner and some remaining charge. The erase station, not shown in Figs. 1 and 5, consists of a ood exposure of the photoreceptor performed by a suitable light source. This step is designed to discharge the photoreceptor and residual toner as completely as possible so that the toner may be removed more easily from the photoreceptor and a consistent initial state may be prepared for the charging subsystem. Cleaning, illustrated schematically in Fig. 9, is performed using one or more of a number of technologies. It is common in many printers to use an elastomer blade to scrape the toners o without damaging the surface of the photoreceptor. Biased cleaning brushes rotating in contact with the photoreceptor belt also are used frequently. The collected toner is placed into a waste toner bottle, to be recycled later. Perhaps the highest goal for cleaning subsystems is to eliminate them entirely by designing transfer subsystems that are suciently ecient, thus enabling a lower machine price by reducing both the cost and number of required subsystems. This is currently one of the greatest technical challenges facing a prospective surface scientist working on xerography.

Fig. 8. Schematic diagram of a fusing subsystem based on using a release agent. The release agent coats the heated fuser roll so that the toner does not stick to the roll. Under the inuence of heat and pressure in the fuser, the toner particles are fused together (i.e., the toner powder becomes a thin polymer lm) and xed to the paper as described in Fig. 11.

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Fig. 9. Schematic diagram of a brush cleaning subsystem. By either mechanical or electrostatic forces, the residual toner is stripped of the photoreceptor and collected in a waste bottle (not shown).

4. Material challenges in xerography: the surface connection As noted above, much of the functional performance of the xerographic process is generated by the use of sophisticated materials packages, typically multi-component organic composites, which must satisfy many constraints. Due to their composite nature, interfacial properties play a dominant role in their performance and stability. The specics vary with the nature of the materials package, with multi-layer systems, lm composites, and multi-component powders being three broad material classes exhibiting distinct design rules and criteria. Photoreceptors (Fig. 2) and fuser rolls (Fig. 8) are two prominent examples of multi-layer mostly organic composites. Both embody sophisticated boundary layer treatments to ensure the mechanical integrity of the device under hostile operating conditions (e.g., heat, corona charging, media contact and release and repeated exion and tension). Wear is a central concern for bothdue primarily to media contact for the fuser rolls but also due to the transfer and cleaning subsystems for the photoreceptor. Moreover both must exhibit good release properties: the photoreceptor to release toner powder in the transfer step and the fuser roll to release melted toner on the media upon exit from the fuser. Finally, the electrical, optical, and thermal properties of these devices must be designed carefully. Fuser rolls need adequate thermal conductivity. Charges generated in the charge generation layer (CGL) of a photoreceptor must cross multiple interfaces and move through the device to discharge the receptor upon exposure. All of

these functional requirements require exquisitely designed interfacial properties both between the various layers of the photoreceptors and fuser rolls and between the base polymer and its loading material for the CGL. Developer and toner powders (Fig. 6) have dierent design criteria. The toner and carrier coating must exhibit the correct magnitude and kinetics of contact charge exchange: very delicate surface properties. They must ow well in powder form for the developer subsystem to work. The toner must exhibit viscoelastic ow when subjected to heat and pressure in order to get a good x to the paper, a suitable gloss on the image, and the reduction of light scattering within the fused toner layer to acceptable levels for transparencies. The humidity sensitivity (i.e., dependence on adsorbed water) of the toner powder ow and contact charge exchange must be controlled. All of these characteristics result from controlling the surface and interface properties of the external and internal surfaces in the toners and carriers. We develop this theme in the following section by considering three specic examples in more detail.

5. Microscopic control of organic composites 5.1. Multi-layer photoreceptors The dual-layer photoreceptor design shown in panel (a) of Fig. 2 is based on separating the functions of photogeneration and charge carrier transport. This allows the exibility to select photogenerator materials optimized for dierent wavelengths of the light sources used in xerography (e.g. visible LED image bars, IR diode lasers) while designing the rest of the photoreceptor to satisfy other constraints on its behavior (e.g., wear, speed, stability). The current trend is toward the use of organic photoconductors. The substrate can be a metal drum or a exible metalized polyester belt, as shown in Fig. 2. The substrate is coated with an undercoat (blocking) layer which serves to prevent the injection of charge carriers in the dark from the grounded electrode. The CGL consists of pigment particles dispersed in a polymer binder. The pigment is selected and optimized

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for the specic application. Some of the pigments used include perylenes, phthalocyanines and azo compounds [2,6]. The function of the thin CGL (about 0.22 lm) is to absorb the incident light and photogenerate charge carriers eciently. The photogenerated charge carrier must be injected and transported through the next layer to reach the surface of the photoreceptor. The charge transport layer (CTL) is coated on top of the CGL and consists of a lm (1530 lm thick) of insulating polymer doped with charge-transporting molecules. Most of the active molecules, which include aryl amines and hydrazone, transport only holes and the photoreceptor surface is charged negative. The CTL should be transparent to the incident light and the layer is designed to be clear and amorphous. Additional layers are included in practical photoreceptors, e.g., an adhesive layer on the metalized polyester to improve adhesion of belt photoreceptors and polymer overcoats on top of the CTL to extend the life of the photoreceptor. The basic phenomena in the operation of the organic photoreceptors are the photogeneration, injection and transport of charge carriers. Detailed descriptions of the design and operation of these devices have been given in Ref. [2]. Surface and interface science plays a key role in the design of practical photoreceptors. The CGL is typically a pigment dispersed in a binder, which requires control of the pigment/binder interfaces for eective photogeneration. The injection of holes into the CTL and electrons into the ground electrode requires engineering of the electronic properties of the CGL interfaces. The adhesion of the CTL, CGL, and backplane layers typically is achieved by special interfacial chemical treatments. Polyesters, polyamides, poly(vinyl butyral), poly(vinyl alcohol), polyurethane, and polyacrylonitrile have been used as adhesives in contact with the supporting substrate. The adhesive layer is of a thickness from about 0.001 lm to about 1 lm. This layer may also contain conductive and nonconductive particles, such as zinc oxide, titanium dioxide, silicon nitride, and carbon black to provide desirable electrical and optical properties [12]. Often the top surface of the photoreceptor is coated with an overcoat designed to reduce the wear on the photoreceptor

by the charging, transfer, and cleaning subsystems and to increase the charge acceptance from the charging subsystem. Thus, the solution of practical surface and interface science problems lies at the foundation of the technical issues associated with fabricating cost-eective, long-life commercial multi-layer photoreceptors. 5.2. Dry ink: conventional and chemical toner Conventional toners are fabricated by dispersing pigments in a polymer base, grinding and classifying. Descriptions of their design and processing are available in the literature [7]. Chemical toner represents a major advance over conventional processing. This new chemical technology involves molecular design and micro-fabrication allowing precision manufacturing of custom toner particles on the micrometer scale. Particle size distribution and surface characteristics are strong drivers of image quality. Narrow size distributions and spherical particles have more uniform charge per unit mass Q=m and hence, more predictable behavior in the development subsystem. Conventional toner manufacture yields a wide distribution of particle sizes and a particle morphology characteristic of broken glass with jagged edges. Chemical toner technology permits the manufacturer to specify a narrow distribution of nearly spherical particles produced by the process, as well as a wide range of materials compositions. A number of chemical toner processes have been commercialized. Among these are suspension polymerization, emulsion aggregation (EA), solvent dispersion, and encapsulation. We discuss here EA as practiced by the Xerox group, Nippon Carbide and Konica [1315]. The EA process is a powerful technology to produce monodispersed composite particles from the submicron to the micrometer range. Controlled aggregation of submicron polymer latex particles, together with pigment particles, is an important process in the development and production of toners as indicated in Fig. 10. Starting from a latex suspension, larger aggregates of well dened size and narrow size distribution form under moderate shear with various additives. The nal aggregates are heated above their glass transition temperature to coalesce, followed by

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Fig. 10. Schematic diagram comparing fabrication of conventional toner to that of chemical toner. The various steps of both fabrication processes are indicated in the gure. The dierences in the morphologies of the resulting toner particles are evident in the pictures at the bottom of the gure.

washing and drying for use as toners. The particle properties, as well as the sizes and size distributions, depend critically on the aggregation process, as controlled by surfactants and additives that modify their interfacial properties. The observed dependencies of the nal aggregate size on process parameters such as initial latex particle size, ionic strength, and ratio of cationic to anionic surfactants can be explained by taking into account the kinetics of aggregation, and using a charged liquid droplet model for the aggregate energetics [16]. The morphology of EA toner particles depends in a complex way on the conditions used during the coalescence of the latex aggregates. The coalescence portion of the EA toner making process involves converting the tightly bound aggregates of latex and pigments into particles that can be employed in the xerographic process. The coalescence of latex particles in a drying paint lm is perhaps the phenomenon having most in common with the EA latex coalescence process. Primary aggregates approximately 1 lm in diameter can contain between 100 and 200 latex particles for

a latex 200 nm in diameter. A toner-sized secondary aggregate of diameter 5 lm would contain about 100 primary aggregates or 15 000 latex particles. The advantages of the EA process to make chemical toner are small toner size, narrow particle size distributions, tunable morphology, wide materials design latitude, and low cost. The particles are ner and more uniform in size and shape compared with the crushed multi-component toner particles. These qualities are important for obtaining more eective development and image transfer. Therefore they yield superior image quality in the xerographic process. The controlled and adjustable modication of the interfacial properties of these specially designed materials using surfactants and additives makes this quality improvement possible. 5.3. Fuser components Roll fusing involves the melting, coalescence, and spreading of toner particles, as well as the

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the treatments of the surface layers of the fuser rolls for release, for studying the chemical reactions of release agents with the fuser roll and toner surfaces, and for providing the specialty adhesives needed to hold the layers of the fuser and donor rolls together under adverse operating conditions. Detailed examples of several applications of interface science studies for the design of multiplayer organic components for fuser and transfer subsystems are given by Badesha and Swift [18]. As noted earlier, this is an arena of major opportunity for the next generation of applied surface scientists.
Fig. 11. Diagram of the physical processes involved in fusing. These are shown as they occur after the toner on the paper enters the fuser as indicated in Fig. 8 (adapted from Ref. [2]).

6. Semiconductor processing connections While most xerographic components involve organic composites, the revolution in the size and performance of semiconductors also is aecting xerographic marking engines. The most important of these inuences are the use of laser diodes in the exposure subsystem, the use of ink jet arrays to mark directly on the output media, and the increased use of active feedback in xerographic process control. In this section we explore some of the impacts of the semiconductor process revolution on xerographic marking engines. 6.1. Semiconductor diode lasers In high-speed printing tradeos are required between high resolution, high speed, and manufacturing tolerances. Fig. 4 shows a raster output scanning illuminator subsystem with a polygon scanner photoreceptor and laser system along with scanning and correction optics. High resolution requires large polygon facets, on the other hand, whereas high speed is advantaged by having many facets. The use of multiple beam diode lasers is able to circumvent part of this tradeo by allowing higher speeds to be attained with fewer facets. In addition, as higher resolution becomes more important, it is advantageous to go to shorter wavelengths, so that higher resolution can be achieved with small polygon facets and good depth of focus. Alternatively, short wavelengths can be used at todays resolution of 600 dpi to increase

adhesion of toner to paper and the cohesive strength of toner, relative to its adhesion to the fuser roll as indicated in Fig. 11 [2]. The important variables in the melting, coalescence, and spreading of toners are temperature, time, pressure, viscosity, particle size, and the surface tension of toner [2,9,10,17]. In particular, adhesion of an image to a substrate depends on the surface energies, the contact area between the surfaces, the toner modulus, the hardness and the brittleness of the toner. In general, coalescence and toner fusion is increased proportional to the pressure, surface tension and dwell time and inversely proportional to the viscosity and particle size. One important variable aecting coalescence is the melt viscoelasticity. External additives on the fuser roll, such as silicone oil, assist in releasing the toner. These additives can, however, increase the coalescence temperature in some toners, which can cause toner aggregation and hence grainy images: not a desirable outcome. The eect of additives such as waxes in the toner can also enhance toner release from the fuser roll and reduce or eliminate the necessity of using oil in the fusing subsystem. In general, materials screening for fusing involves initially selecting the viscoelastic properties of toner resins for optimum fusing performance, and then studying the eects of various additives such as surface charge control agents on fusing. Interface science provides the foundation for designing

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the speed of a printing system by using a large number of smaller polygon facets. A Moores law type assessment reveals that print resolution for oce printers is doubling about every 12 years and that 1200 dpi is upon us. A blue laser print engine operating at a resolution 1200 dpi enables oset quality xerographic printing at high speeds provided that a photoreceptor with suitable spectral sensitivity becomes available commercially. IIIV compound semiconductor materials for semiconductor diode lasers are prepared by metal organic chemical vapor deposition (MOCVD). In this technique the group 3 species (aluminum, gallium, indium) are transported into a growth chamber as the vapors of organo-metallic precursors e.g. trimethylgallium. The group 5 species, however, are transported as hydrides for example arsine, phosphine, or ammonia. The development of this technique was a triumph of surface science in the 1970s [19,20]. Laser diodes are fabricated from materials of exceptional structural and optoelectronic perfection. Structural defects (such as dislocations) or impurities can seriously degrade the luminescence eciency of semiconductor materials. Thus, the materials from which laser diodes are made start with single crystal substrates to ensure that the deposited lms are as structurally perfect as possible. As indicated in Fig. 12, red and near-infrared

lasers are grown on gallium arsenide single crystal substrate wafers, ber optic devices are deposited over indium phosphate substrates, and nitride lasers are deposited on sapphire substrates. Nitride laser structures dier from infrared or red laser diodes in a number of important respects. IR and red lasers, used today in xerographic marking engines, are grown perfectly lattice matched, on gallium arsenide substrates [21]. Therefore the dislocation density is very small, representing the defect density of the substrate seed crystal. On the other hand, nitride laser structures are most often deposited on sapphire substrates, corresponding to a 14% lattice mis-match, which produces an enormous defect density [22]. Such a large concentration of defects would render IR or red emitting materials optically inactive. The nitrides apparently do not suer from these dislocations, however, a surprising fact that is still under investigation. The ongoing development of nitride lasers is a frontier in modern materials and interface science, which directly impacts xerographic marking technology [23]. 6.2. Microelectromechanical systems (MEMS) markers The eld of MEMS, deals with micron scale machining, mechanical functionality, and low

Fig. 12. Schematic diagram of the MOCVD fabricated blue (left-hand panel) and red (right-hand panel) laser diodes for xerographic exposure systems. The emission of light from the active region is indicated by a green arrow. The dierent layers of these diode lasers are indicated. The geometry is simplied relative to that of a production laser. The structures are comprized of epitaxial layers of single-crystal material. Dierent active layers are required to generate light in dierent spectral regions: GaAs for IR and InGaN for blue. Dierent substrates are required in order to get suciently accurate lattice matching for adequate epitaxial growth.

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manufacturing cost for a large number of identical parts, as well as enabling high-bandwidth mechanical behavior [24]. An example is a thermal ink jet (TIJ) head that integrates electronics and sensor actuator functionality, and uses polymers in a large area application. MEMS technology already has exerted a profound impact on the printing industry by virtue of its use to generate an unprecedented cost/performance ratio for TIJ products that currently dominate the desktop color-printing market [25]. The two main performance qualiers for printing products are image quality and print speed. One approach to increasing print speed is through an increasing number ejectors per print head, economically enabled through a high degree of modularity and integration, including on-chip addressing logic. In terms of image quality, a high integration level enables ever-increasing image resolution. The implementation of this strategy relies on MEMS technology to combine uid ow pathways, ejector nozzles, uid reservoirs, heater elements, MOS power drivers and addressing logic onto one silicon die. In the Xerox process [26] TIJ die are fabricated by wafer level bonding of a bulk micromachined silicon channel wafer to an MOS heater wafer with an intermediate polyimide spacer layer. The wafer bonding is based on a thermal cure adhesive process. The channel wafer contains the uid ow channels and local link reservoirs, micromachined using wet anisotropic etching of crystalline silicon. The front face is subsequently coated with hydrophobic lm to avoid ooding by the ink. The heater wafer is a MOS wafer that contains 128 polysilicone heater elements (one per channel), addressing logic, driver circuitry and power switches. The integration of these elements with on-board uidics requires several microelectronic process and device design tradeos. The adoption of batch fabrication technology to produce disposable print heads has changed the rules of the desktop color-printing market, launching low end printing products onto cost and performance trajectories that are analogous to semiconductor industry trajectories. The technology consists of a unique blend of large-scale

integration (LSI), microuidics and thermodynamics. This integration requires design compromises to be made across various energy domains (e.g., electrical, thermal, mechanical, chemical), and various technologies (e.g., MOS, micromachining, ink, and paper). Yet the eciency of the batch fabrication techniques is suciently high for disposable print heads to be economically viable. The design, manufacture and commercial introduction of such disposable heads illustrate well the complexity of the processes and devices to which modern applied surface scientists are making major contributions. 6.3. Sensing and control Even with all the emphasis on reproducibility of the process and the materials components, external disturbances still cause the quality of the printed output to vary. Variations in temperature, humidity, toner consumption, and media composition all lead to corresponding variations in the appearance of the output prints. For monochrome printing, image quality stabilization was resolved using simple algorithms and a few sensors. In color printing the subsystem latitudes that produce predictable color images are more restricted, and output variations much less tolerable. The products of semiconductor processing have been utilized to mitigate this problem in two specic ways. Firstly, the sensors that are used to detect variations in the intermediate and nal process outputs require increasing levels of integration. Their functions include sensing, calibration, networking, timing, and recently, considerable computation. The sensor device is self-contained including the sensing element, drive electronics, communications, computation, and memory all coresident. These levels of integration may be obtained using assemblies but are increasingly implemented using MEMS processing for the sensing element and compatible CMOS processes for the other components. A preliminary example of this type of integration is the spectrophotometer produced by MicroParts [27]. It has an optical input and integrates a MEMS fabricated diraction grating coupled to a CCD array for spectral discrimination

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and detection. The output of the sensor is an array of numbers corresponding to the visible spectrum of the light at the optical input. Secondly, with inexpensive sensors providing frequent, accurate, and calibrated readings and the performance of semiconductor chips constantly increasing, sophisticated process control algorithms running in standard commercial semiconductor processors become feasible. Ten years ago with 8 bit devices even elementary arithmetic operations (e.g. oating point division) occupied 10s of milliseconds (ms). The dwell time for sensed features on the photoreceptor is less than 5 ms for even moderate speed printers. Thus, the feature could pass under the sensor without being detected because the processor was busy doing division. Real-time sensing and computation was impossible. Now matrix inversion, Fast Fourier Transform, and other complex computations may be performed in less than 1 ms and may be interrupted by real-time events in multi-tasking environments. This capability, thanks to the results of Moores law, has been combined with the last three decades of advances in automatic control theory to provide both the algorithms and the computational environment to compute process adjustments in real time. These adjustments alter the behavior of the xerographic system to provide disturbance rejection resulting in consistent, predictable image quality from a very complex colorprinting system [28]. This trend of using MEMS devices as sensors, actuators, and mechanically functional units plus the application of the computational consequences of Moores law will continue with the result that more commercial semiconductor devices will be integrated into future photocopy machines and printers.

7. Direct marking and the future of xerography Perhaps the greatest competitive challenge to xerography in the digital era is its replacement by smaller, simpler and hence less expensive direct marking devices. Direct marking involves replacing the charging, exposure and development subsys-

tems shown in Fig. 1 with a direct marking head that writes on a consumable such as paper, or an intermediate belt or drum from which the image is transferred to the consumable medium. Commercially successful direct marking engines have fewer parts, less weight, smaller footprints, and simpler architectural design than their xerographic counterparts. This technology also oers a potential cost advantage of direct marking inks with respect to xerographic developer, one for achieving liquid ink/lithographic document appearance and image quality, and the prospect of easier maintenance with fewer replacement parts. For the time being, however, they operate at slower speeds and with generally lower image quality than xerographic printers. One approach to improving the image quality and extending the range of media for both xerographic and direct marking is by exploring marking engines in which the marker produces an image on an intermediate belt or drum from which it is subsequently transferred and fused to the nal medium in a single transfuse step. In the Oce printing scheme [29], an intermediate transfer medium can be preheated to the toner melting temperature at the print fuser, and in one belt revolution the page panel scrolls through the highpressure fuser, handing the image o to the consumable media (e.g., paper or transparency). In this technology, the imaging of the toner exiting the direct marking head is always carried out on the intermediate transfer medium eliminating substrate variability (e.g., dierent papers, transparencies). After the toner is imaged on the intermediate transfer medium, it is fused and transferred at the same time to the substrate. Hence the substrates can encompass a wide range of paper weights, nishes, and coatings. This type of subsystem, in which transfer and fusing are thus combined, is a current frontier in xerographic marking. The belt can be heated because it does not come into contact with a temperature-sensitive element like a photoreceptor. An addition, the subsystem can deliver a very thin layer of a release agent to the belt [30] before it comes in contact with the imaging material (toner), enabling ecient release of the toner from the intermediate transfer medium, which can be in the form of an endless belt [29]. Obviously, the

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design of the toner, the intermediate medium and the transfuse subsystem process depend sensitively on the surface and interface properties of the toner and medium, and their dependence on temperature. It is evident, therefore, that the solution of surface and interface science problems plays a major role in the design and implementation of such transfuse subsystems. Historically, xerography rose to commercial prominence because of its unique suitability to make black and white (monochrome) copies via light-lens exposure. The digital era has fundamentally changed its competitive positioning. First, color, unachievable at adequate image quality with lightlens exposure, is enabled by the use of digital scanners and color-correction software. Second, the use of digital originals in printers and copiers has obviated the competitive advantages of lightlens xerography and rendered direct marking engines competitive with xerographic marking engines. At the desktop, where acquisition cost is king, slow speeds are tolerable, and image quality can be good enough, color TIJ marking directly on paper have captured the market. In the high volume, multiple-copy markets (e.g., magazines, newspapers) lithography has been king for many years. Thus, color xerography is sandwiched in the middle, advantaged relative to each by special features (e.g., speed and image quality relative to TIJ and short-run cost and variable data capability relative to lithography) but ghting for its share of the short-run digital color-printer/copier market. The winners and losers in this competition will be determined largely by the speed and ecacy of the solution of sophisticated surface and interface problems associated with the toners or inks and their interactions with both the image bearing media and the various surfaces with which they come in contact during the marking process. Long life, low cost and high image quality require sophisticated consumables that reduce the complexity of the marking engine by assuming added complexity in the materials themselves. In each market space the race will be won by the marking technology that yields solutions most quickly to the shortfalls in areas of high customer value. For direct marking devices, key issues include image quality, image permanence, and range of output

media. For xerography they are cost, media latitude, and in some markets image appearance relative to lithography. For lithography they are short-run cost, automation of setup and maintenance of high image quality, and suitability for oce environments. Progress on all of these rests on surface and interface science because in all cases the results are dominated by the consequences of the interactions of the ink or toner with the surfaces that they touch during the course of the marking process. For direct marking, the ink media interaction is the key to image quality and permanence. For xerography, lowering the cost and improving the reliability of the process requires ever more sophisticated multi-component photoreceptor, toner, carrier and fuser materials packages. For lithography, process control via sensors and electronics and euent control are key issues. All of these are dominated by mediamaterials interactions driven by surface and interface phenomena. Thus, we can condently anticipate that in the future, as in the past [1,2, 610], the solution of challenging applied problems in surface and interface science by talented and creative surface scientists, will enable the inexorable march of color-marking engines, xerographic as well as others, to better, faster, cheaper.

8. Synopsis The amazing development of the xerographic copier and printer industries since the 1950s has been a direct consequence of sustained investment in basic research underlying the Xerographic process and associated materials [3]. It resulted from the diligent, systematic application of physics, chemistry and surface science, leading to wealth for investors and excellent careers, sometimes even recognition and fame, for the scientists and engineers who pioneered the major advances. The advent of the digital, networked era has changed the calculus relative to the stand-alone lightlens copier era (195585), rendering other marking technologies more competitive in certain market segments. Commercial success in this new era depends even more upon exploitation of the fruits of research in surface and interface science, than

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in the copier era. There is a continuing big payo for applications of surface and interface science in the printer/copier industry and a generous supply of as yet unsolved problems to challenge the next generation of creative applied scientists and engineers.

References
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[14] H. Shimomura, Y. Hasegawa, H. Serizawa, M. Masatoshi, Toners for developing electrostatic image, US Patent 5,591,556, Jan. 7, 1997. [15] M. Koyama, K. Hayashi, T. Kikuchi, H. Yamazaki, Toner for developing an electrostatic latent image, Developer and a method of producing an image using the toner, US Patent 5,830,617, Nov. 3, 1998. [16] N. Bohr, J.A. Wheeler, Mechanism of nuclear ssion, Phys. Rev. 56 (1939) 426. [17] D.A. Seanor, Fusing against bare metal surfaces, Photo. Sci. Eng. 22 (1978) 240. [18] S.S. Badesha, J.A. Swift, Practical surfaces: beyond the wheel, Surf. Sci. 500 (2002) 1024. [19] A.Y. Cho, Preparation and properties of GaAs devices by molecular-beam epitaxy, J. Electrochem. Soc. 122 (1975) C262. [20] J.R. Arthur, Molecular beam epitaxy, Surf. Sci. 500 (2002) 189. [21] R.S. Geels, D.F. Welch, D.R. Scifres, D.P. Bour, D.W. Treat, R.D. Bringans, Dual spot visible laser diodes, Electron. Lett. 28 (1992) 1460. [22] S.D. Lester, F.A. Ponce, M.G. Craford, D.A. Steigerwald, High dislocation densities in high eciency GaNbased light-emitting diodes, Appl. Phys. Lett. 66 (1995) 1249. [23] R.D. Bringans, Application of blue diode lasers to printing, Mat. Res. Soc. Symp. Proc. 482 (1998) 1203. [24] E. Peeters, Micro electro mechanical systems: pyrite or pure gold?, APS News 8 (1999) 5. [25] M.P. OHoro, N.V. Deshpande, D.J. Drake, Drop generation processes in TIJ printheads, in: Proceedings of the 10th International Congress on Advances in Non-Impact Printing Technologies XXX, Society for Imaging Science and Technology, 1994, p. 418. [26] E. Peeters, S. Verdonckt-Vandebroek, Thermal ink jet technology, IEEE Circ. Dev. 13 (1997) 19. [27] VIS-LIGA-Spectrophotometer for Analysis and Color Measurement, STEAG MicroParts GmbH, Havert 7, Dortmund D-44227, Germany, 2000. [28] T.E. Thieret, T.A. Henderson, M.A. Butler, Method and control system architecture for controlling tone reproduction in a printing device, US Patent 5,471,313, Nov. 28, 1995. [29] H.A.M. Loonen, M. Miedema, B. Schoustra, J.A. Verbundt, E.H.A.M. Smit, Toner image transfer apparatus including intermediate transfer medium, US Patent 5,361,126, Nov. 1, 1994. [30] J.S. Berkes, J.S. Chambers, Brush for applying release agent to intermediate transfer member, US Patent 5,434,657, Jul. 18, 1995.