The application of plasma physics to the manufacturing and processing of
materials may be the ...... one could perhaps engineer a discharge that is better
suited.
Industrial Francis
applications
of low-temperature
plasma physics*
F. Chent
University of California, Los Angeles, California 900241594
(Received14 November 1994; accepted6 February 1995) The applicationof plasmaphysics to the manufacturingand processingof materials may be the new frontier of our discipline. Already partially ionized discharges are used in industry, and the performanceof plasmashas a large commercialand technologicalimpact. However,the scienceof low-temperatureplasmasis not as well developedas that of high-temperature,collisionlessplasmas. In this paperseveralmajor areasof applicationare describedand examplesof forefront problemsin each are given. The underlying thesis is that gas dischargeshave evolved beyond a black art, and that intellectually challenging problems with elegant solutions can be found. 0 I995 American institute of Physics.
1. INTRODUCTION
During the past four decades, the science of hightemperatureand collisionless plasmashas grown explosively, fueled by the challenging problemsin magneticfusion, inertial fusion, and space plasma physics. As funds for basic researchin fusion and spaceplasmasdwindle, it is fortunate that a new application of plasma physics has loomed large within the past five years-that of the use of lowtemperature,partially ionized plasmasin manufacturingand materialsprocessing.Indeed, this aspect of plasma physics may ultimately be the one with the greatestimpact on our everydaylives. Although industrial applicationshave drawn great interest in plasma physics-the number of paperspublished monthly on plasma-relatedtopics in semiconductor processingalone far exceedsthe numberin fusion researchat its peak-the field has not benefitedfrom the expertiseof the cadreof physicists who have honed their skills in the classical areasof plasma physics. Gas dischargesare viewed by them as being an empirical discipline, devoid of elegance and beset with unnecessarycomplications. The purpose of this paperis to show that intellectually challengingproblems can be found in low-temperatureplasmaphysics, and that the complicationsof high collisionality and multiple speciesmay be no more complicated and resistantto treatmentthan, say, instabilities in toroidal magnetic fields. The subject is very broad;and with due apologiesto all the scientistsworking in this field, we must limit our coverageto a few representative examplesin each case.The succeedingsectionswilI discuss semiconductorprocessing,flat panel displays, ion implantation, plasma polymerization and coating, thermal plasmas, and basic physics of low-temperatureplasmas. II. SEMICONDUCTOR A. Physical
mechanisms
PROCESSING in etching
The productionof integratedcircuits consistsof repeated stepsof deposition, masking, etching, and stripping to form and connectcircuit elementslike transistorsand capacitors. Hundredsof chips can be made simultaneouslyon a silicon *Paper 9RV. Bull. Am. Phys. Sot. 39, 1749 (1994). %&ted speaker.
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Phys. Plasmas 2 (6), June 1995
wafer, which is typically 4-8 in. in diameternow and lo-12 in. in the near future. To put some five million transistorson a Pentium chip, for instance,the individual elementshave to be below 0.5 ,um in size and moving toward 0.25 pm. Such resolution cannotbe achievedwithout a plasma.All computers and other electronic devicesof the future will dependon plasma processing; yet, at the moment, very few plasma physicists have been involved. The plasma is neededfor etching in at least three ways: (1) it producesthe atomic species,usually Cl or F, which does the etching; (2) it preparesthe substratesurfaceso that the etchantspeciescan be more effective: and (3) it provides the directionality that allows the etching to proceed in a straight line. The plasmadoes not always have to touch the surface to perform its functions. The symbiosis between a plasma and an etching gas was demonstratedin the classic 1979 experimentof Coburn and Winters’ (Fig. 11,in which they showedthat the etch rate of fluorine in an argon plasma was over an order of magnitudelarger than with either the gas or the plasma alone. In addition to the etch rate, the plasma also provides profile control-the ability to etch a trench with straight sidewalls. Purely chemical etching would undercutthe mask and producea trench with rounded corners.By acceleratingions through a sheath,one can make them impinge on the mask and substrate at right angles, therefore affecting only the surface at the bottom of the trench, not the sides. This is known as anisotropic etching. However, isotropic chemical etching is still present to degrade the trench profile (Fig. 2). By a fortunate accident, someof the etch productsform a plastic polymer that deposits on the trench walls and protects them from the chemical etchant, unless they are cleanedby a flux of energeticions. Only by carefully balancing this “passivation” mechanism and the plasma-enhanced etch rate can one produce a square trench profile2q3(Pig. 3). Four types of materialsneedto be etchedin Ultra LargeScale Integration (ULSI) processing:silicon (monocrystalline or polycrystalline, doped or undoped),dielectrics (usually Si02 or SiN,), metals (usually aluminum, tungsten,or molybdenum),and photoresist.Each of theseinvolves different chemistries and different groups of experts. The processesthat follow are not necessarilythoseused in any actual production line but will serve to give the flavor of what is
1070-664)(/95/2(6)/2164/V/$6.00
0 1995 American Institute of Physics
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h+Ion Beam + XeF, Gas 4
/
?54 3I3 38
RESIST
l : 32 I
1 1
0
L
0
100
200
300
400
500
6CKL
700
800
900
L
Time (set)
FIG. 1. Evidence for the catalytic effect of plasma on chemical etching [reprinted with the permission of the American Institute of Physics (Ref. I)]. OXIDE
involved.4Silicon can be etched by either fluorine or chlorine. In chlorine etching, the plasmafirst dissociatesCl, into Cl atoms.Thesereact with Si to form SiCl, and SiCl,: Si+2 Cl-SiCl,, Sic&+2 C1--+SiC14. Here SiCl, is a gasand can be pumpedout. In addition,-SiClz polymerizes to form [SiC12],, the passivation agent. If needed,the amountof SiC12can be increasedby addinghydrogen: SiC1,+2 H+SiClz+2 HCl. Oxide is also etchedby F and Cl, but more slowly than silicon is. For instance,with fluorine.?we could use a CF4 plasma: CF4+2 F+CF, (monomer),
ai.r; Si02+4 F-iSiF4+2 0 (gases), ?1 Si02+2 CF&GF4+2 CO (gases).
-_r _,.I., Meanwhile,the silicon is being etchedfaster by the reaction ..
Si+4 F-+SiF,.
lsotropif2 etch
Noions
Directional etch -~
ions, no passivdoo
Vertical etch
With passitiation
PIG. 2. Square trench profiles require both directional ion flux and passivation with polymers [reprinted with the permission of the American Institute of Physics (Ref. 2)].-
Phys. Plasmas, Vol. 2, No. 6, June 1995
PIG. 3. Variation in trench wall profiles produced by changing the plasma parameters and chemistry [reprinted with the permission of Academic Press (Ref. 3)].
If one wants to etch Si preferentially,one can add oxygen, which frees up more fluorine by combining with the atoms that :fluorine would. otherwise combine with.. However, to etch SiOz faster than Si, one has to add hydrogen, which decreaseswith fluorine content by forming the stable compound HF. This is tricky, becausetoo much hydrogenstops the etching altogetherby forming polymers, and the best selectivity for anoxide etch is just short of this poim4 Aluminum, the most common conductor,is etchedby chlorine, but only after an ‘%icubationperiod,”during.whichthe protective aluminum oxide layer is etched away. This layer is alwaysXformedbecauseoxygen comes into the discharge from the quartzor glasswalls. Photoresistis an organicpolymer,which can be etchedby oxygen and fluorine, or stripped by a wet chemicalprocess.The selectivity in etching photoresist versus.Si is .of the order of 5, whereasthe Si/SiO, .selectivity can ‘be of the order of 100. _(Lr_ ..: B. Forefront
problems.
in etching
’
(1) RIE lag and microlo&ding.5. Reactive Ion Etching (RIE) lag is the dependenceof the etch rate on the shapeof the pattern being etched. For instance, deep trenches are etchedmore slowly than shallow ones, probablybecauseof the depletionof the necessary,chemical speciesnearthe bottom. Though -namedfor the RIE’discharge (defined later), this can occur with any plasma source. Microloading is- a related effect, also due to depletion,in which the etch rate dependson the proximity of neighboringfeatures.It is not clear how a plasmacan be designedto avoid this depletion other than by making it denser.’ (2) Particulates. It has been known for some time that dust particles B 1 pm in size are formed from the gasesused in etching or deposition6(Fig. 4). These particles are negatively chargedto the potential of a floating Langmuir pro!: and are suspendedin the plasmaat local potential maxima ’ (Fig. 5). Though Selwyn’has shown that theseparticles can be pushedalong equipotentialsby the neutral gas, they cannot be eliminated,and still are a big problem inthe semiconFrancis F. Chen
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FIG. 4. Photomicrographs of micron-sized dust particles [Part (a) reprinted with permission of Institute of Physics Publishing (Ref. 7) and Parts (b) and (c) with the permission of Institute of Physics Publishing (Ref. S)].
ductor industry. The potential traps tend to be at the sheath edgejust above the wafer, and the particles fall into the wafer at plasma turnoff when the sheathcollapses.The chips that are destroyed significantly decreasethe yield and increase the cost of a chip. A remedy for this has been investigated.”By placing metal and dielectric inserts under the wafer, the potential contours in the plasma can be changedto remove the potential traps.The behaviorof dusty plasmasprovides a connectionbetweenplasma processing and the astrophysicsand spaceplasmaphysics community. (3) Device damage. The thin oxide layer that insulates the gate of a Metal Oxide Silicon Field Effect Transistor (MOSFET) or such device has to be as thin as possible; pinhole-freeoxide gatesas thin as tensof angstromsare now possible. However, if electrostatic charges from energetic electronsor ions should accumulateon the surface of the oxide, the large electric field across the dielectric would drive thesechargesinto its interior and becomepermanently imbedded,rendering the device useless.There is evidence that device damagemay occur during plasmaturnoff, is correlatedwith density gradients,and hencepotential gradients, acrossthe wafer,” and is increasedby magneticfields at the wafer,” but there is not yet a full understandingof the mechanism.To avoid damageduring etching or deposition, one can put the wafer downstreamfrom the plasma source and use the source only to createthe necessaryatomic species, but it would clearly be preferableto tailor the plasma parametersso that damagedoes not occur. (4) Electrosfatic chucks. Since the plasma heats the Si wafer (which is a relatively poor thermal conductor) during processing,it is usually necessaryto cool it with a flow of helium underneath.The surfaceroughnessof the undersideis enoughto allow the helium to flow betweenthe wafer and the chuck. Wafers are usually clamped at the edge, but as wafer diametersbecome larger, the expansionof the wafer causesit to bulge out and changethe flow of helium. Thereis 2166
Phys. Plasmas, Vol. 2, No. 6, June 1995
current activity to developelectrostaticchucks that can hold the wafer flat electrostaticallyand still allow adequatecboling. It is not clear that this problem has to do with plasma physics. (5) Neutral beam etching. The problem of device damage can be avoided if the directional ions are replacedby directional neutral particles.Though the parameterregime is quite different, neutral beamsourcesare prevalentin the fusion community, and some of this expertiseshouldbe applicable to the developmentof neutral beam etching reactors. (6) LOW-E dielectrics. Finally, there is an interest in developing new insulatingmaterialswith a low permittivity. In fact, a variety of permittivities would be useful in future design of optical computingchips (see Sec. V). C. Dense
plasma
sourcesi3~24
The most obvious need for plasma physics in plasma processingis in the production of the plasma. There is in-
FIG. 5. Laser-illuminated dust clouds electrostatically trapped in ring- and dome-shaped regions above three round wafers in an etching reactor [reprinted with the permission of the American Institute of Physics (Ref. 6)].
Francis F. Chen
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tense current activity in the development of dense plasma sourcesthat can increasethe etch or ,depositionrate. An ideal source should have the following characteristics. (i) lJniformity over n large area. It is clearly more economical to put a large wafer through the same number of steps than a small one, but this requires plasmauniformity to the order of 23% over the entire diameter.It is said that the only difference betweencomputer chips rated at, say, 50 and at 66 MHz is that they come from different parts of the same wafer; those near the edge are not made as accurately and must be rated at a lower speed.Density uniformity also implies potential uniformity and straight ion orbits; (ii) Simplicity and compactness. Since hundreds of processing machinesmay be employed at a single manufacturing plant, a large premium is placed on simplicity, compactness,and reliability of the plasma source.Laboratory sources with long magnetic fields, for instance, would not be commercially viable becauseof. the space they occupy &d the power they would consume: (iii) High density at low pressure. Typical processing reactors operate with plasma densities in the low IO” crne3 range. New sourcesbeing developed would bring the average density up to the 10” cme3 range, increasing the etch rate by an order of magnitude.A higher ionization efficiency also permits operation below 10 mTorr, thus decreasingthe likelihood that an ion would suffer a &&ion in the sheath before reaching the substrate. (ivj High eficiency. Current parallel-plate reactors require only hundredsof watts of RF power and no’magnetic field. Higher-density sources may require more than 1 kW and magnetic field power in addition. The Electron Cyclotron Resonance(ECR) source, for instance,requires an 875 G magnetic field. Ideally, any new source should create higher density without a proportionate increase in power consumption. s. (.v) Straight ion orbits with controllable epergy. For profile control, ions are acceleratedin a sheath, whose voltage drop is set by the DC potential applied to the etched surface. Since the latter is not always a good conductor, this dc potential is createdby applying an RF voltage to the substrate and using the unidirectional electron flow to charge the substrate negatively. In parallel-plate discharges,this RF bias cannot be controlled independently,since increasing the applied RF voltage increasesthe density and other parameters also, with the resuIt that the ion energycan be too large. In inductive and ECR sources,the plasma is ionized independently of the substrate’s RF bias, and .i?n energies of the desired value-say 15-50 eV--can be applied. Uiiifo&y of the plasma near the wafer edge should also be maintained to keep the sheathfield perpendicularto. the surface. (vi) Controllable electron energies. An ideal source should also afford some degree of control over the electron temperature and distribution function in order to affect the molecular species being produced. Furthermore, fast electrons, such as runaway electrons in an ECR dischargeat low pressure, should be avoided in order to minimize Vacuum Ultraviolet (VUV) and x-ray production and device damage. (vii) Good selectivity. Each reactor made for a particular process is. optimized to give the necessaryselectivity bePhys. Plasmas, Vol. 2, No. 6, June 1995
He coolant ’ Bias RF -
/,,/Powered electrode
, 1 ,Gas in’et
Main RF ,
J
‘1’
f
._
Gas outlet i.
LlG. 6. Schematic of an parallel-plate capacitive discharge.
tween the materials being etched. A good plasma source should be flexible enough to be used for different applica.,tiohs. (viii) Benign materiaZS. Only a-few materials are permitted iti an etching chamber: Si, Al, and W or MO. Quartz or glass walls contain Si, which is not a contaminant,and oxygen, which is neededfor passivation.Aluminum is permissible as a conductor becauseit is protected from the Cl or F etchant by its own oxide layer, tid W or MO is attackedonly slowly. A plasma sourcewith external electrodesis therefore preferred. Here we give a brief description of the most popular plasma sources. (a) Reactive Ion Etcher (RIE). Shown in Fig. 6, this is simply an RF discharge between two^~parallel plate electrodes, on the lower of which the substrateis clamped. The RF .power is usually applied to the upper pltite, while a smaller RF bias voltage is applied to the substrate.The DC bias- resulting. from both sources can’be several hundred volts; creating a Child-Langmuir sheath over a cm thick, much thicker than the Debye sheath:At the industrial standard frequency of 13.56 MHz, the ions fall steadily through this sheath with only a small modulation in velocity at -the RF frequency.Becauseof its simplicity, this type of sourceis used in the vast majority of semiconductorfabrication lines. Modifications of this sourceare being evaluated.MERIE is a Magnetically EnhancedRIE. The hollow cathodesource is a symmetrically driven RIE with a perforated plate at the ground-potentialmidplane. Small dischargesin the holes initiate the ionization process. (b) Electron Cyclotron Resonance(ECR).15A spinoff from the technology developedfor ECRF heating of fusion plasmas,these 2.45 GHz sources (Fig. 7) have been used in a variety of ways, from close-coupled diamond-deposition machines with a resonance(w=w,) layer close to the substrate to ‘a downstream reactor, in which the plasma is expandedinto a uniformizing chamberwith permanentmagnet multidipole confitiement. The source can produce high density at low pressure,and is preferred for some processesby the Japanese,who hold most of the patentson ECR reactors. (c) Transfomzer Coupled Plasma (TCP). I6 Developed Francis F. Chen
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Quartzwindow -,
Microwave
Gas1
Plasma stream\
SOURCESOLENOID
Vacuum $ l-+b
g;rLEi
FIG. 7. Schematic of an ECR plasma source (reprinted with the permission of Plenum Press).
specifically for producing large-areaplasmas,these devices have a flat coil, shapedlike the heating coil on an electric range,on top of the processingchamber,separatedfrom it by a quartz plate and sometimesalso a slotted Faraday shield (Fig. 8). The coil appliesan azimuthalRF electric field to the gas, breaking it down and forming a plasmajust under the quartz plate. The plasma diffuses downward to the wafer. The patent is held by Lam ResearchCorp.,17which has begun marketing TCP reactors. Intense activity has recently begunon the modeling of this new device. (d) Radio-Frequency Inductive (RFI).16 This is essentially the same as the TCP, except for the shapeof the cross sectionof the RF coil. Researchon this device was done at IBM.” (e) Helicon Wave Source (HWS).*9 This relative newcomer employs an external antennaof varying design and a dc magnetic field to excite a propagatinghelicon wave, a cylindrically confined low-frequencywhistler wave (Fig. 9). The wave efficiently ionizes the plasmawith usually l-2 kW of RF power.This type of dischargeproduceshigher densities at the sameRF power level than other RF sources,2o for RF Power In-,
SUBSTRAEWATERCOOLING
FIG. 9. Schematic of a helicon plasma source [reprinted with the permission of the American Institute of Physics (Ref. 20)].
reasonsthat are not yet clear. It is thought that primary electrons are acceleratedto ionizing energiesby wave-particle interactions,but this has not been confirmed experimentally in a convincing manner.Though most experimentationis on the m= 1 azimuthal mode of the helicon wave, the m =0 mode has been successfully used in a source marketed by PlasmaMaterials Technologies,Inc., with many of the ideal featureslisted above. (f) inductively Coupled Plasma (ICP).‘6 This is an RFexcited plasmaemploying a helical antennawound arounda cylindrical dischargetube. Direct electrostatic coupling is usually avoidedby addinga Faradayshield. The RF doesnot excite a resonantwave as in the helicon source,but nonetheless a fairly high density of uniform plasmacan be produced. D. Numerical
Gos Inlet
FIG. 8. Schematic of a RF inductively coupled discharge [reprinted with permission of Institute of Physics Publishing (Ref. 16)].
2168
Phys. Plasmas, Vol. 2, No. 6, June 1995
modeling
Different techniquesare neededto model the plasma sources,the chemical and surface interactions, and the microscopic processesin the etching of patterns.Modeling the plasma is usually done with hybrid codes, which treat the plasmaas a fluid, exceptwhereparticle kinetics is necessary, such as in reactive colIisions2’Other packagesthat treat the antennacoupling and external circuitry, the collision cross sections,the chemical reactions,etc. are coupled to the fluid model. Two-dimensionalcalculationsare now standard.The RIE and ECR dischargeshave beenmodeledextensively by many groups2’and are the best understoodof the various Francis F. Chen
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sources.Modeling of the TCP and RFI sourceshas recently drawn the attention of several groups.23-25 The modeling of helicon.and other inductive sourceshas not yet received intensive treatment. What occurs on a surface when it is attackedby plasma and corrosive gasesis best seenin molecular dynamics simulations in which each atom is followed and the intermolecular forces are taken into account in detail. This promising techniqueis computer intensive, and only a few studieshave been made so farZ6 Similarly, Monte Carlo computations have to be used to treat ‘RIE lag and microloading in patterned wafers.
E. Diagnostics
Light Source
and sensors
The difference between a diagnostic and a sensoris that while a diagnostic can be a complicated and expensivepiece of equipment used in the laboratory, a sensor is a simple, cheap, and foolproof device used on a production line. For example, a commonly used sensoris the end point detector, which spectroscopicallydetectsthe presenceof, say, a Si line to show when one has etched through to the silicon. New, reliable sensors are in great. demand for -monitoring the manufacturingprocessand for quality control. In the laboratory, a large number of diagnostic techniques from both plasma physics and chemical engineering have been used. Some of these and their acronyms are now listed. Laserinduced fluorescence (LIF) and multiphoton variations of LIF; electron spectroscopyfor chemical analysis (ESCA); optical emissionand absorptionspectroscopy[VUV, UV, visible, infrared (IR)]; attenuated total internal reflection; micro-Raman scattering; Fourier transform infrared (FTLR) absorption spectroscopy; infrared diode laser absorption: resonance-enhancedmultiphoton ionization spectroscopy (REMPI); high resolution electron energy loss spectroscopy (HREELS); mass spectrometry (MS); low-energy electron diffraction spectroscopy (LEEDS); film interference measurements; x-ray photoelectron spectroscopy(XPS); Auger electron spectroscopy(AES); and coherent anti-Stokes Raman scattering (CARS). Though the list is long, there is still a need for developing new diagnostics for detecting the many physical and chemical processesinvolved in plasma processing.
F. Deposition,
OFF
cleaning,
and stripping
PlasmaEnhancedChemical Vapor Deposition (PECVD) and other deposition processesare at least as important as etching, but we have not specifically discussed them, becausethe same kinds of plasmas are involved, and there are fewer problems of plasma physics interest in deposition than in etching. Stripping of photoresistand cleaning of substrates (and of spacecraftpanels)can be done with plasmas,but they are commonly done by wet chemistry. In the long run, however, dry processingwill prevail becausethe other steps demand plasma processing, and because the environmental problem of liquid wasteswould be avoided. Phys. Plasmas, Vol. 2, No. 6, June 1995
’ ! Transparent Electrode ‘Polarizer (mlyzing)
1 Polarizer (Polarizing) ‘Transparent Electrode
FTG. 10. Mechanism of a liquid crystal display [reprinted with the permission of O’Mara Associates and Van Nostrand Reinhold (Ref. 28)].
Ill. FLAT PANEL A. Principles
DISPLAYS
of flat-panel
display
technology27728
We are just at the threshold of this industry, which is predicted to grow many-fold over the next ten years. The cost of color flat-panel displays (FPDs) is at the moment so high that the market is driven by applications that can stand the expense:portable computers,camcorderviewfinders, and aircraft cockpits. Cathode ray tubes (CRTS)are the standard to which new displays are compared,but FPDs, being more compact and energy efficient than CRTs, will eventually replace the CRT, much as the transistor has replaced the vacuum tube: As the price of color FPDs drops, we can expect to see them used in desktop, as well as notebook, computers; in high-definition television (HDTV); and in automobile and aircraft dashboards,where a myriad of dials can be replacedby a single panel on which any information can be called up, including maps and other navigation aids. The highest resolution being shown now is only 1280X 1024 pixels (times 3 or 4 for color), which is crude compared with ULSI chips; and for this reason,wet processing,rather than plasma processing,is used for most of the steps.Eventually, however, the industry will be driven to the use of plasmas becauseof the need for speedand the environmental impact of liquid wastes.The goal of the Active Matrix Liquid Crystal Display (AMLCD) industry is to produce 60 plates per hour per fabrication line, which would not be possible without faster etching with denseplasmas. To illustrate the problems in designing FPDs, consider a simple liquid crystal (LC) display (Fig 10). Imagine a layer of liquid crystal material, perhaps0.1 mm thick, placed between two vertical glass plates, each covered with polarizing material. Backlight from a fluorescent source goes through the right polarizer, and its polarization is changed.90”by the Francis F. Chen
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Horhanw Elactrcd~
for a gray scale:light must be transmittedat different intensities Furthermore,a capacitorshould ideally be attached acrosseachpixel to that the appliedvoltageis held until the next sweep.Clearly, theseconnectionsbetweenthe plates would be impossibleto align. Spacershaveto be introduced to keepthe platespacinguniform. TheseproblemsaresoIved in AMLCDs, which use plasmasonly in fabrication,and in other devicesthat use the Z-V characteristicsof the plasma itself to providethe memorybetweenframes. There are other problemsthat display systemsneedto dealwith. Electricalefficiencyis especiallyimportantin portablecomputers.Here,the m a inpowerconsumptionis by the backlight, which alreadyutilizes the high efficiency of fluorescentlights. The viewing angleis a problem with LCDs; theseare alreadyoptimizedto provide a greaterhorizontal than vertical angle, and there are proposalsto divide each pixel into severalpixels, eachaimedin a different direction Televisiondisplaysare more difficult to designthan m o n itor displays,becausethe signal must decayfast enoughto portray rapid motion. Contrast, gray scale, and visibility in bright light are other criteria. F inally, simplicity, reliability, ruggedness, and cost are the ultimate market considerations. B. Active
matrix
liquid
crystal
(AMLCD)
displaysz8
Many of the problemslisted above are solved in the active-matrixsystem,in which a thin-film transistor(TFT) is m a d e at one corner of each pixel. Both the rows and the columns are depositedon the bottom plate. The top plate is 2811. grounded,and the voltageon the LC is switchedon andoff by the TFT. Since the signalsneedbe applied only to the LC. The left polarizeris orientedso that the light doesnot go high-impedancegate of the TIT, the problems with throughthe top plate. W h e n a horizontalelectric field is ap- feedthroughor decayof the signal betweensweepscan be phed to the LC material, its crystalsalign themselveshorisolved.The driver circuits handIea low-powerlevel, andno zontally, allowing the light to pass.The LC is then divided interconnectionsneedto be m a d ebetweenplates.W ith the into pixels by rows of conductorsin the x direction on the exceptionof specialkinds of glass, polycrystallinesilicon right plate and columnsof conductorsin the y direction on (p-Si) cannotbe depositedon the glasssubstratesbecauseof the left plate (Fig. 11).A voltage,say -5 V, is appliedsuc- the high temperatures required,andthereforeamorphoussilicessivelyto eachof the bottom rows, completinga sweepof con (a-Si) is used.The m o b ility in a-Si is too low for makthe whole frame every 60th of a second.The datasignalsof, ing driver circuits but is sufficient for the relatively crude say +5 V, are applied to the top cohnnns,turning on the TFTs. This meansthat, for the moment, the driver circuits properpixels at the propertime. The conductorson the top must be on a separatechip that is connectedto the rows and plate must be transparentand are usually m a d eof indiumcolumns.In the future, one hopesto have all the driver cirtin-oxide (ITO). For color, the pixels are in groupsof three cuits, pixels, TFTs, and interconnectsall fabricatedat the or four [RGB (red-green-blue) or RGBG], each with an sametim e on the samesubstrate.Note that the spacersfor alignedcolor filter. Each of the rows and columns is con- the liquid crystal gap can be depositedalong with the TFTs, nectedto a driver circuit, which appliesthe requiredvoltandthat the aperturetakenup by theseopaqueobjectsis only ages.Thereare clever m u ltiplexingschemesthat reducethe a small fraction of the total pixel area.Amorphoussilicon numberof connectionsnecessaryand also the information has to be hydrogenated to improvethe electronm o b ility by that needsto be transmitted;for instance,only thosepixels removingimpurity traps. Plasmaprocessingcan be usedto that are to be changedon eachsweepneedto be addressed. speedup and improvethe quality of the deposition,etching, Making electrical connectionsto both platesmakesas- ion doping,and hydrogenation processes. In displaysas well semblydifficult. There is also the problemof feedthrough: as in ULSI chips,contaminationby dust is a m a jor problem; the signal can couple throughthe capacitanceof one pixel the ultimate cost is sensitiveto the yield,29and too many into a neighboringpixel. To avoid this, the LC material inoperativepixels can make a display unacceptable. At the shouldhave a sharpcurrent-voltage(Z-V) characteristic,so moment,color AMLCDs are lim ited to about9 in. in diagothat it is insensitiveto voltagessmaller than the intended nal length,cost about$1000each,andarealmostexclusively one. Supertwistednematic (SIN) materialswere developed manufacturedin Japan.There is room for improvementon for this purpose.At the sametime, theremust be a provision all counts. FIG. 11. Schematic of a Super-misted Nematic LCD (passive matrix) and a Thin-Film Transistor (active matrix) LCD display, showing the difference in electrode configuration. The liquid crystal layer is not shown [reprinted with the permission of O ’Mara Associates and Van Nostrand Reinhold (Ref.
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Francis F. Chen
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C. Plasma-addressed
liquid
crystal
(PALC)
displays30
A new system under developmentby TechnicalVisions, Inc., replacesthe TFT switches of the AMLCD with glow dischargesand avoidssilicon technologyaltogether.The row electrodesare now conductingstrips depositedinside semicircular groovesabout 0.3 m m wide etchedinto the bottom glass plate. A secondstrip electrodeinside each groove is connectedto ground. The voltage to be applied acrossthe LCs is applied to column electrodeson the upper plate. The row electrodesare floating in the off state, but when a voltage pulse is applied to them, the gas in the groovesbreaks down into a transverseglow discharge,and the row electrodes are groundedthrough the plasma,turning on the pixels. Once such a dischargeis initiated, it takes much less voltage to maintainit. This is a plasmaswitch; a backlight is still neededto view the LCs. For television applications, there is a problem of making the dischargesdecay fast enoughto give the requiredfrequencyresponse.A m ixture of gasesis used that strikes a compromiseamong breakdown voltage, decay time, and sputtering.damageto the groove walls. The engineeringof this display makes direct use of low-temperatureplasmaphysics. D. Thin film electroluminescent
(TFEL)
displays27
An electroluminescentmaterial gives off light when a voltageis applied.Robustand requiring no backlighting,this type of display was one of the first flat-paneldisplaysmade. Developmentof TFEL displaysis actively being pursued,but so far the fabrication processhas little to do with plasmas. E. AC plasma
displays
(ACPD)
A plasma display has‘pixels each of which acts like a m iniature fluorescent lamp. When a high-pressureneonargondischargeis struck in the pixel, ultraviolet light is generated,and this is convertedinto visible light with good-&ficiency,just as in fluorescentlights. Different phosphorsare used for color, and no backlight is required. The preferred method is to useAC rather than DC excitation.An AC voltage is applied between the row electrodeson the bottom plate and the column electrodeson the top plate. The plasma cells are coatedwith an insulatinglayer of magnesiumoxide, which providesthe memory mechanism.Once the discharge has beentriggeredon by a pulse,the chargesthat accumulate on the dielectric are sufficient to reignite the dischargeon the next half-cycle of the AC; thus, the dischargeremains on until a signal comesalong to kill it. It is clear that theselittie dischargescannot be made small enough to make a highresolution monitor display, but they are ideal for the large displays used for presentationsor wall-hung television screens,which would be hard to make with liquid crystals. Full color AC plasma displays of 30-40 in. diagonal have and recently a 21 in. diagonalcolor been demonstrated,31732 TV display has been shown that usesthis technology,32 F. Field emission
displays
(FED)
Arrays of m icrotips can be etchedin MO, togetherwith holes centeredon these in an anodeplate above them by a Phys. Plasmas, Vol. 2, No. 6, June 1995
Extracted Ion
BePm
,~’ G-4
Ezz”zy 1 ,!
Vacuum Positive Ions Strike AU Surfaces at Normal Incidence
.@) Vacuum ’ FIG. 12. In ion beam implantation (a), the object must be rotated to exppse the surfaces to be implanted. In PSII (b), a plasma covers the object, and ions are accelerated onto a11surface by the sheath drop [reprinted with the permission of J. Conrad (private communication, 1994)].
self-maskingprocess.Thesetips are so sharpthat field emission can occur for potentialsas low as 50 V.33The electrons go through the anodeholes, sometimesafter passingthrough a control grid, and strike phosphorsto producelight of different colors as in a cathoderay tube (CRT). This conceptof a flat-panelCRT has not beendevelopedas far as the others, but the activity is increasing.There are questionson sputtering and lifetime of the m icrotips and on the best operating voltage. It may be possible to make the m icrotips out of diamond.In that case,plasmaprocessingmay be called for, though it has not beenused so far. IV. PLASMA
SOURCE
ION IMPLANTATION
(PSll)34
Implantation of nitrogen and other atoms deeply into a surfacecan greatly improve suchpropertiesof the surfaceas hardness,friction, and resistanceto wear and corrosion.This can be done in two ways: by energetic ion beams of the implantedatom, or by immersingthe object in a plasmaof the implantedspeciesand giving the object a -50 kV pulse, say, to acceleratethe plasmaions through a sheath(Fig. 12). If the sheathis thin, the plasma will surroundan object of irregular shape,and the object does not have to be turned to exposeall of its facesto the ion beam.PSI1is not only faster, but also simpler. Examplesof its use can be found in the hardeningof cutting tool tips, the improvementin friction and wear of artificial knee joints, the corrosion proofing of concretereinforcementbars, and the surfacing of magnetic and optical disks. The power supplies for PSII are rather large: >50 kV at 50 A and 2 kHz. Many papershave been written on the design and switching of such supplies.35To Francis F. Chen
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make the situation worse, there is the problem of secondary emissionfrom the target. The secondaryelectrons go to the anode(the walls), and not only do they heat up the walls, but their current also has to be provided by the power supply.To alleviate this problem, magnetic insulation has been suggested,36 but this may be difficult to implement for complicated shapes.It is clear that thin sheathsare desirablefor perpendicularacceleration of the ions into the workpiece, and denser plasmas will give thinner sheaths. The dense plasmasourcesbeing developedfor etching can also be applied to PSII. Thus, there are a number of interestingplasma problemsconnectedwith this process. V. PLASMA
POLYMERIZATION
AND COATING
Organic coatings applied with plasma have a number of applications.37 (i) Barrier coatings. Leakprooling of common containers can be done by exposing their interiors to a CF, plasma. Gas tanks can be made impervious to gasoline (though, curiously, not to methanol); and plastic soft drink bottles, for instance,can be made more impervious to the outward diffusion of CO2 and the inward diffusion of 02. Medical capsules are another example. The exteriors of containers can also be treated with plasmasto improve their adhesion,usually by adding a NH, group to the polymer chain. For instance,potato chip bags can be printed, and car bumperscan be painted more easily after plasma treatment. (ii) Fibrous materials. Both wool and synthetic fibers can be colored more easily after being immersedin a plasma. Wood and paper are other fibrous materials commonly treated. Filter paper and rainwear can be made less absorbent, and diapers can be made more absorbentby plasma treatment, in this case by adding an OH group to the moleculesby exposure to an HDMSO plasma. (iii) Optical coatings and optical jibers. Deposition of dielectric layers of different indices of refraction has long been done by sputtering. It is now possible to do this by PECVD, and special plasmascan be developedfor this purpose. (iv) Integrated optics for optical computing. A future prospectis the integration of optical componentsinto computing chips. In this case there would be a need for plasma depositionof polymers of varying index of refraction in the manufacturingprocess. (v) Cleaning and sterilization of biomedical surfaces.
Another application on the horizon is the sterilization of medical containers and the cleaning of surfacesexposedto dangerousbiomedical substances.Though cleaning with liquids is always possible, plasma processingwould lower the volume of toxic wastesthat have to be disposedof. (vi) Plasma polymerization.38 This is an active research area at present, but the large commercial impact is yet to come. When monomers are polymerized into a plastic layer without plasma, the polymer chains tend to be aligned with one another.However, when the polymerization is done in a plasma,the polymer chains are highly cross-linked,resulting in a plastic that is much stronger than usual. The most common substancetreated this way is plasma polymerized methyl methacrylate (PPMMA). MMA is a commonly known 2172
Phys. Plasmas, Vol. 2, No. 6, June 1995
Plasma Cathode CH,+ H, Gas, ?,,,
A&de
Non-LTE BoundarvIaver Substrate FIG. 13. Schematic of a thermal plasma jet [reprinted with the permission of J. ffender (private communication, 1994)].
as Plexiglas or Lucite. Researchon plasma polymerizationis being done with the various plasmasourcesdiscussedbefore, including ECR and RFI sources. It is not known why the plasma has its beneficial effect; almost certainly, the breaking of bonds by the electronsplays a role. One of the goals of the research is to understandthe reason for the crosslinking by detecting the precursorsof the final product. Optimization of the process is difficult becauseof the many variables involved. One has to understandthe roles of the plasmadensity, electron temperature,operating pressure,and RF frequency on the one hand, and of the gas mixture, flow rate, and substrate temperatureon the other. To make the processmore amenableto practical application, severalsteps can be taken. One is to invent devices to form a polymer layer on the inside of containersand on convoluted surfaces. Another is to treat continuouswebs of material on a moving belt. Perhapsone can invent new plastic materials that are more easily recyclable. VI. THERMAL
PLASMAS3’
Thermal plasmas are a generic term for high-pressure plasmasthat are so collisional that the particles and gasesare in thermal equilibrium, though the radiation is, of course, not. Spray treatments of turbine blades and other airplane and automobile parts to harden the surfaces is already commonplace. In fact, the manufacture of wire-arc sprays and other such equipment is a billion-dollar business. Unfortunately, not much of this money goesinto research.The future lies not so much in the continued improvement of these devices but in finding new and exciting applications for them. For instance,diamond deposition is best done with thermal plasmas becauseof their high densities. Figure 13 shows such an apparatus.It has recently been found that the adhesion of a diamond coating can be strengthenedby depositing a metal layer when the diamond crystals are half-grown, and then continuing to grow the crystals on top of the layer (Fig. 14). With a cheap method for diamond coatings, we can imagine that all cutting and sanding tools of the future will be so treated, and will hardly ever wear out. Since diamond Francis F. Chen
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dischargescould have a transition betweencollisional and collionless damping at a particular radius. Using this effect, one could perhapsengineera dischargethat is better suited f for the task at hand:: 1 (2) Radiation transport in high-pre&re plasmas. At Step 1: diamond deposition on substrates high pressuressuch as exist in fluorescentlamp discharges, by plaSma CVD the propagationof ionization energyproceedsnot by.electron Metal binder diffusion through the neutral gas, but by the diffusion of resonantphotons (of-energf equal to the energy of the first excited state), which have a longer meanfree path than the Step 2: electroplating of metal binder electrons.This effect has already been studied extensively, but the computationsare difficult becauseresonantradiation doesnot have a single frequency.To accountproperly for the changein Spectrumlateach collision requiresnew and more powerful computationaltechniques.4zPlasmasin which energy transportis dominatedby radiation is a new frontier of Step 3: re-growth of diamonds research. (3) Multistep iofzization processes. Multiphoton ionization is well known in laser experiments,but in gas discharges multistep ionization can occur through the formation of FIG. 14. hletbod for improving the adhesion of diamond films by deposition of a metal binder during an interruption of the growth process [reprinted metastables.This mechanismmay the dominantone in some with the permission of E. Pfender (private communication, 1994)]. discharges.A related topic. is the Penning effect-the in,.. creasein ionization in gas mixtures due to the coincidenceof energy levels in the different atoms. Though Penningmixes is unusualin being a good heat conductor and a good elecare well known and can be bought commercially, there has trical insulator at the sametime, it may replacesilicon as the been no detailed understandingof why they are effective. A preferredsemiconductorsubstrate.Thermal plasma research better understandingmay lead to the ability to engineergas can also lead to new methodsin metallurgy.Wastetreatment mixtures that are-evenmore efficiently ionized. with plasmasis not glamorous,but an increasingly~important (4) Transit-time heating in sheaths. In dischargeslike the potential application.But perhapsthe most exciting prospect RIE, the sheathsoscillate violently, so that electronsdipping is the creation of new materials with thermal plasmas,matein and out of the sheathcan pick up energy if they enter in rials such as p-CsN, and cubic boron nitride (cBN), which the right phase.This has beenrecognizedas one mechanism are reputedto be even harder than diamond. for .electron heating in such discharges.The problem is analogousto that of transit-time magnetic pumping, which VII. BASIC LOW-TEMPERATURE PLASMA PHYSICS was treatedby the magnetic fusion community a long time ago. Though low-temperature,partially ionized plasmas are (5) Elec&n runaway in RF discharges. An interesting complicated by the existence of several, sometimes many, positive and negativespeciesof particles with different cross experimentby Sakawaet a1.43in Japanconcernsthe formasections, they are usually free ‘of complicated magnetic tion of. pairs .of bright rings in a pulsed RF hydrogen disfields. Comparedto fusion-relatedplasmas,low-temperature charge,a phenomenonfirst found by a group in Florida. The RF is coupled~to the cylindric.al plasma chamber by two plasmashave received little attentionfrom the plasma community, though serious thought is being given to the plasma externalconductingrings about 10 cm apart.As the pressure is increased,,a pair of bright rings is seen at the midplane in the divertor region of tokamaks.There is little doubt that (Fig. 15). At higher pressure,three ring pairs appear,then interesting problems can be formulated and solved, which five, and,so on. The rings are more sharply defined than now seemas intractableas toroidal magneticfields did in the striations in glow discharges.It is easy to see why the rings 1950s.We cannot predict what problems will arise, but we can give here a sample of what problems can be seentoday. appearin pairs: each ring of the pair is producedduring a different half-cycle of the RF, and indeed, optical emission (1) Kinetic effects in low-temperature plasmas. In the high-efficiency sourcesbeing developed,the operatingpresshowsthat the rings have*oppositephases.At a pressureof 3 sure can be as low as 1 mTorr, and Coulombcollisions domiTorr and above,however,it is difficult to seehow an electron can gain enoughenergybetweencollisions to excite an atom. nate over collisions with neutrals. The plasma can then be treatedas a fully ionized plasma.At plasma densitiesbelow We believe that this could be an example of electron runaway in RF discharges.The runawayphenomenoncannotbe about 1013cmV3,kinetic effects should be observable.It has seenin DC dischargesbecausehigh electric fields causethe been suggested,for example,that the high efficiency of the helicon sourceis due to Landaudampingof. the waves,” and dischargeto turn into an arc. However, in RF discharges large E fields can be applied without arcing. An important some experimentsreport the observationof high-energytails in the electrondistribution.41Definitive experimentshave not clue is that the rings are seenonly in hydrogen.Most atoms yet been performed. Kinetic effects should occur preferen- have a peak in their electron impact cross sections at low tially in the low-density regions near the boundary,so that energies, and runaway cannot occur becauselow-energy Diamond particles _-. Substrate
Phys. Plasmas, Vol. 2, No. 6, June 1995
Francis F. Chen
2173
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ventedby Dawsonand developedby TRW, Inc.“’Thoughthe separationof uranium by this method is no longer funded, the processwill work for any element.There is a need for medical isotopesproducedthis way. Dischargeswith different elementswould have to be developed.Another isotope separationprocessis Atomic VaporLaser IsotopeSeparation (AVLIS), which is basedon selective ionization of one isotope by laser light.46Once ionized, the separatedions must be driven out of the plasma and collected. To speedup the collection process,Japaneseresearchershave tried heating the electronsto increasethe ion acousticvelocity and cyclotron heatingthe ions in a magneticfield. Thus, the problems are not laser problems,but real plasma problems. VIII. CONCLUSION
AND ACKNOWLEDGMENTS
In conclusion, we hope that these exampleshave given an idea of the excitement in the developing field of lowtemperatureplasmaphysics and of the opportunitiesfor applying to this field the techniqueslearnedin studying hightemperatureplasmas. ACKNOWLEDGMENTS FIG. 15. Discrete ring pairs seen in a high-pressure RF discharge [reprinted with the permission of Y. Sakawa (Ref. 43)]. The number of pairs and their positions change with pressure, as shown in the graph.
electronsseea rising cross sectionas they gain energy.However, hydrogenhas a monotonicallyfalling cross section(the cross section at low energy being enhancedby dipole interaction), and could supportrunawayelectrons.This is an example of a detailed experimentthat needsa good theory. (6) RF and microwave discharges for lighting. Highpressuredischargesfor the lighting industry is an area of researchthat is active, but not so active as to justify a separate section. The fluorescentlamp has a surprisingly high efficiency@ (65% conversion of electricity to UV) which probablycannot be further improved, but work is still being doneto understandthesedischarges.At the sametime, there is demandfor new light sourcesbasedon microwave or RF excitation. For military applications, extremely bright and efficient lighting is neededfor large areas,and for the home market the absenceof internal electrodesmay make a light bulb both long-lived and efficient. Though many inventions have been made, none, as yet, has been commercially successful that is not a variety of the fluorescentlight. (7) Effective use of instabilities. Normally, instabilities are undesirable,but in nonfusionapplicationsone may actually wish to excite instabilities.For instance,if one wantedto make an intense electron beam sourceout of a magnetized RF discharge,there would be no problemextractingthe electrons, but ions would also have to be extracted in order to keep the plasma neutral. In that case,it would help to have an instability drive the ions out in anotherdirection. Similarly, in the AVLIS schemedescribedbelow, an instability could be used to extract the ions more rapidly. (8) Lsotope separation. The PlasmaSeparationProcessis an isotope separationschemebasedon selective cyclotron accelerationof ions of a certain mass.This processwas in2174
Phys. Plasmas, Vol. 2, No. 6, June 1995
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