U.S. patent application number 12/404472 was filed with the patent office on 2009-09-03 for reversible photo bleachable materials based on nano sized semiconductor particles and their optical applications.
This patent application is currently assigned to PIXELLIGENT TECHNOLOGIES LLC. Invention is credited to Zhiyun Chen, Gregory D. Cooper, Erin F. Fleet, Serpil Gonen.
Application Number | 20090220756 12/404472 |
Document ID | / |
Family ID | 32511599 |
Filed Date | 2009-09-03 |
United States Patent
Application |
20090220756 |
Kind Code |
A1 |
Chen; Zhiyun ; et
al. |
September 3, 2009 |
REVERSIBLE PHOTO BLEACHABLE MATERIALS BASED ON NANO SIZED
SEMICONDUCTOR PARTICLES AND THEIR OPTICAL APPLICATIONS
Abstract
Semiconductor nano-particles, due to their specific physical
properties, can be used as reversible photo-bleachable materials
for a wide spectrum, from far infrared to deep UV. Applications
include, reversible contrast enhancement layer (R-CEL) in optical
lithography, lithography mask inspection and writing and optical
storage technologies.
Inventors: |
Chen; Zhiyun; (Silver
Spring, MD) ; Fleet; Erin F.; (Springfield, VA)
; Gonen; Serpil; (College Park, MD) ; Cooper;
Gregory D.; (Arlington, VA) |
Correspondence
Address: |
NIXON & VANDERHYE, PC
901 NORTH GLEBE ROAD, 11TH FLOOR
ARLINGTON
VA
22203
US
|
Assignee: |
PIXELLIGENT TECHNOLOGIES
LLC
College Park
MD
|
Family ID: |
32511599 |
Appl. No.: |
12/404472 |
Filed: |
March 16, 2009 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10730382 |
Dec 9, 2003 |
7510818 |
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12404472 |
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60431735 |
Dec 9, 2002 |
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Current U.S.
Class: |
428/206 ;
252/503; 356/432; 428/195.1; 977/773; 977/811; 977/814; 977/816;
977/818; 977/819; 977/823; 977/824 |
Current CPC
Class: |
Y10S 430/146 20130101;
G02F 1/015 20130101; G02F 2203/12 20130101; G02F 2202/36 20130101;
G03F 7/70383 20130101; B82Y 20/00 20130101; G02F 1/01716 20130101;
Y10S 977/932 20130101; Y10T 428/24893 20150115; Y10T 428/24802
20150115; G02F 1/0126 20130101; G03F 7/70291 20130101 |
Class at
Publication: |
428/206 ;
252/503; 428/195.1; 356/432; 977/814; 977/811; 977/816; 977/818;
977/819; 977/823; 977/824; 977/773 |
International
Class: |
B32B 5/16 20060101
B32B005/16; H01B 1/22 20060101 H01B001/22; B32B 3/10 20060101
B32B003/10; G01N 21/00 20060101 G01N021/00 |
Claims
1. A reversible photo-bleachable material comprising semiconductor
nano-sized particles.
2. The material of claim 1 wherein said semiconductor comprises: C,
Si, Ge, CuCl, CuBr, CuI, AgCl, AgBr, AgI, Ag.sub.2S, CaO, MgO, ZnO,
Mg.sub.xZn.sub.1-xO, ZnS, HgS, ZnSe, CdS, CdSe, CdTe, HgTe, PbS,
BN, AlN, GaN, Al.sub.xGa.sub.1-xN, GaP GaAs, GaSb, InP, InAs,
In.sub.xGa.sub.1-xAs, SiC, Si.sub.1-xGe.sub.x, Si.sub.3N.sub.4,
ZrN, CaF.sub.2, YF.sub.3, Al.sub.2O.sub.3, SiO.sub.2, TiO.sub.2,
Cu.sub.2O, Zr.sub.2O.sub.3, ZrO.sub.2, SnO.sub.2, YSi.sub.2,
GalnP.sub.2, Cd.sub.3P.sub.2, Fe.sub.2S, Cu.sub.2S,
Culn.sub.2S.sub.2, MoS.sub.2, In.sub.2S.sub.3, Bi.sub.2S.sub.3,
Culn.sub.2Se.sub.2, In.sub.2Se.sub.3, Hgl.sub.2, Pbl.sub.2 and
their various isomers and alloys.
3. The material of claim 1 wherein said nano-particles are in
spherical, cubical, rod-like, tetragonal, single or multi-wall
nano-tube or other nano-scale geometric shapes.
4. The material of claim 1 wherein said nano-particles are immersed
in polymer matrix or other chemicals.
5. The materials of claim 1 wherein the nano-particles are doped
with other elements.
6. The materials of claim 1 wherein the nano-particles are coated
with other semiconductors or chemicals.
7. A method of using reversible photo-bleachable material to create
images or patterns with higher resolution than diffraction limit
allows.
8. A method of adjusting the relaxation time of the reversible
photo-bleachable material comprising a mechanism to separate at
least part of the photo-generated electrons and holes.
9. A method of claim 8 wherein said mechanism comprises providing
carrier accepting surface states in said nano-particles.
10. A method of claim 8 wherein said mechanism comprises providing
chemical surfactant at the surface of said nano-particles.
11. A method of claim 8 wherein said mechanism comprises providing
two types of nano-particles with different band-gaps.
12. A method of claim 8 wherein said mechanism comprises providing
coating of another semiconductor with different band-gap at the
surface of said nano-particles.
13. A method of claim 8 wherein said mechanism comprises providing
n-type nano-particle in a p-type polymer matrix.
14. A method of claim 8 wherein said mechanism comprises providing
p-type nano-particle in an n-type polymer matrix.
15. A method of claim 8 wherein said mechanism comprises providing
n-type nano-particle or p-type nano-particles in a non-doped
polymer matrix.
16. A method of claim 8 wherein said mechanism comprises Auger
recombination of multiple electron and hole pairs in said
nano-particles.
17-29. (canceled)
30. A method of inspecting a lithography mask, said method
comprising: providing R-CEL based on reversible photo-bleachable
material on said mask; and photo detectors detecting reflection or
transmission of illumination of said mask.
31. The method of claim 30 wherein said illumination passes though
a layer including said nano-particles before reaching said
mask.
32-33. (canceled)
34. An optical storage device comprising: a substrate having
optically-scannable information-bearing indicia thereon; and a
reversible contrast enhancement layer based on reversible
photo-bleachable material disposed on at least part of said
substrate.
35. The optical storage device of claim 34 wherein said reversible
contrast enhancement layer contains nano-particles.
Description
CROSS-REFERENCES TO RELATED APPLICATIONS
[0001] This application claims the benefit of priority from
provisional application No. 60/431,735 filed Dec. 9, 2002,
incorporated herein by reference.
[0002] This application is related to U.S. Pat. No. 6,291,110 B1,
entitled "Methods for Transferring a Two-Dimensional Programmable
Exposure Pattern for Photolithography"; and commonly-assigned
application Ser. No. ______, entitled "Programmable
Photolithographic Mask Based On Semiconductor Nano-Particle Optical
Modulators" filed concurrently herewith; and commonly-assigned
provisional application No. 60/451,240, entitled "Applications of
Semiconductor Nano-sized particles in photolithography system"; and
commonly-assigned provisional application Ser. No. 60/463,626,
entitled "Methods of Improving Resolution in a Photolithographic
System Using Multi-image Transfer Through Layers to a
Photoresist".
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0003] Not applicable.
FIELD
[0004] The technology herein relates to reversible photo-bleachable
materials. More particularly it relates to the use of semiconductor
nano-particles to provide reversible photo-bleaching. Still more
particularly, one non-limiting aspect relates to provide
applications in photolithography as reversible contrast enhancement
layer (R-CEL) and other uses. Still more particularly, one
non-limiting aspect relates to provide contrast enhancement in
lithographic mask inspection. Still more particularly, one
non-limiting aspect relates to provide contrast enhancement in
optical data storage.
BACKGROUND AND SUMMARY
Photo-Bleaching Process
[0005] A material is opaque to light of certain wavelength because
certain mechanism in this material makes it absorbs photons of that
particular wavelength. The absorption sometime induces the
degradation or saturation of the light absorption mechanism. This
therefore renders the material transparent to the certain
wavelength. This process is called photo-bleaching. Most organic
dyes photo-bleach. For example, the color of hair fades under
prolonged exposure to sunshine.
[0006] For many applications, the photo-bleaching should be
reversible, i.e., the materials recover their original optical
property after the light is turned off. The relaxation process can
happen automatically. It can also be triggered by external
conditions such as electrical or magnetic field, light at different
wavelength, heat, etc.
[0007] The photo-bleaching process has a wide range of
applications. One non-limiting example is the contrast enhancement
material (CEM) in photolithography. The transparency of a CEM
varies directly with the intensity of the incident light. In other
words, its ability to absorb photons decreases as incident light
promotes electrons in the CEM from the ground state into the
excited state. A CEM increases the contrast of the image, resulting
in improved resolution and depth of focus and reduced interference.
These factors in turn allow the fabrication of denser integrated
circuits without additional capital equipment investment.
[0008] FIG. 1 illustrates a prior art contrast enhancing process in
photolithography. The distribution of light intensity from the
laser light usually follows Airy pattern. The width of the central
peak of the Airy pattern is 1.22.lamda./NA, where .lamda. is the
wavelength of the incident light and NA is the numerical aperture
of the optical system. In this illustration, only at the center of
the spot, where the incident light is most intense, can the light
bleaches through the contrast enhancement layer (CEL). Other parts
of the Airy Pattern, including the side-lobes, are filtered out by
the CEL. Light catalyzes the photoresist only in the region where
it bleaches through. Therefore the resulting line width can be much
smaller than the incident wavelength. It is also possible to
produce a light pattern with a width smaller than that of the Airy
pattern at the cost of putting more power in the side lobes. This
is known as apodization. (See co-pending commonly-assigned U.S.
patent application Ser. No. 10/283,322 entitled "Advanced Exposure
Techniques For Programmable Lithography). Apodization can further
increase the resolution with the help of CEM. A review of
strategies for sub-diffraction limit lithography can be found in an
article by S. R. J. Brueck, "International Trends in Applied
Optics", SPIE Press, 2002, pp. 85-109.
[0009] A prior art example is CEM for 365 nm photolithography
manufactured by Shin-Etsu MicroSi. Conventional CEMs, which are
based on organic polymers, however, bleach permanently. They do not
recover their original property after the incident light is turned
off. For lithography processes such as multi-exposure lithography
and programmable lithography, reversible contrast enhancement
materials (R-CEM) are more relevant. With these lithography methods
and a reversible contrast enhancement layer, it is possible to
print features finer and denser than the conventional diffraction
limit can. See U.S. Pat. No. 6,291,110 B1, entitled "Methods for
Transferring a Two-dimensional Programmable Exposure Pattern for
Photolithography"; and commonly-assigned provisional patent
application No. 60/463,626, entitled "Methods of Improving
Resolution in a Photolithographic System Using Multi-image Transfer
Through Layers to a Photo-resist";
[0010] We propose a new type of photo-bleachable and reversible
photo-bleachable materials based on nano-particles of
semiconductors. Such type of materials provides reversibility,
i.e., they can recover their original properties after the incident
light is turned off. Moreover, these materials cover a broad
spectrum of the wavelength from far infrared to deep ultra-violet,
including the entire spectrum of optical applications.
Semiconductor Nano-Particles:
[0011] Nano-particles are loosely defined as powders with diameter
ranging from 1 nm to 100 nm. Since they have only been the focus of
research in the last two decades, they assumes different names,
such as quantum dot, quantum sphere, quantum crystallite,
nano-crystal, micro-crystal, colloidal particle, nano-particle,
nano-cluster, Q-particle or artificial atom. They also assume
different shapes, spherical, cubical, rod-like, tetragonal, single
or multiple-walled nano-tubes, etc.
[0012] Due to their small size, nano-particles often possess
dramatically different physical properties from their bulk
counterparts. Nano-particles have a wide range of applications,
from metallurgy, chemical sensor, pharmaceutical, painting industry
to cosmetics industry. Thanks to the rapid development in synthesis
methods in the last two decades, they have now entered into
microelectronic and optical applications. Nano-particles of a
variety of semiconductors, including those most common ones have
been successfully synthesized. A non-exhaustive list includes: C,
Si, Ge, CuCl, CuBr, CuI, AgCl, AgBr, AgI, Ag.sub.2S, CaO, MgO, ZnO,
Mg.sub.xZn.sub.1-xO, ZnS, HgS, ZnSe, CdS, CdSe, CdTe, HgTe, PbS,
BN, AlN, GaN, , Al.sub.xGa.sub.1-xN, GaP GaAs, GaSb, InP, InAs,
In.sub.xGa.sub.1-xAs, SiC, Si.sub.1-xGe.sub.x, Si.sub.3N.sub.4,
ZrN, CaF.sub.2, YF.sub.3, Al.sub.2O.sub.3, SiO.sub.2, TiO.sub.2,
Cu.sub.2O, Zr.sub.2O.sub.3, ZrO.sub.2, SnO.sub.2, YSi.sub.2,
GalnP.sub.2, Cd.sub.3P.sub.2, Fe.sub.2S, Cu.sub.2S,
CuIn.sub.2S.sub.2, MoS.sub.2, In.sub.2S.sub.3, Bi.sub.2S.sub.3,
CuIn.sub.2Se.sub.2, In.sub.2Se.sub.3, HgI.sub.2, PbI.sub.2 and
their various isomers and alloys. They have revealed very
interesting electrical and optical properties.
[0013] In a semiconductor material, the possible energy states for
electrons are grouped into energy bands. These energy bands are
separated by band-gaps where no electron states are allowed. The
highest populated energy band is called the valence band and the
lowest unpopulated energy band is called the conduction band. When
a photon with energy less than the band-gap that separates the
valence band and conduction band is incident on the semiconductor
material it will not be absorbed. However, if the photon has energy
higher than the band-gap, it will be absorbed by promoting an
electron from the top of the valence band to the bottom of the
conduction band. Meanwhile this process will leave an empty
electron state, a hole, at the top of the valence band. In reality,
the electron-hole pair created by the photon forms an entity
resembling a hydrogen atom, called an "exciton". The Coulomb
attraction between the electron and hole will lower their energy.
Therefore photons with energy slightly less than the band-gap can
be absorbed. The lowest energy where absorption occurs is called
the absorption edge. If all the electron and hole pairs
corresponding to certain photon energy are excited to form
excitons, no more absorption can occur, and the material is
"bleached". Hence semiconductors are bleachable materials.
[0014] Excited carriers in a semiconductor have a finite life-time.
After this time the semiconductor relaxes by recombination of
electrons and holes. Hence after the light is turned off, a
bleached semiconductor can recover its original optical property.
In other word, the bleaching process in a semiconductor is
reversible. The relaxation process can also be triggered by
external conditions such as electrical field, magnetic field, light
with different wavelength, heat, etc.
[0015] The amount of light with a given energy that a semiconductor
can absorb is proportional to its density of states (DOS), that is,
the number of electron and hole states available at this energy.
Semiconductors in bulk and thin film form do not bleach easily. The
bulk DOS is large and requires a high light intensity, it is shown
in FIG. 2a. One way to decrease the density of state is through the
quantum size effects. When the size of a semiconductor becomes very
small, the energy levels of electrons and holes are no longer
continuous. They are quantized into discreet levels. Usually when
the thickness of a thin film approaches several tens of nanometer,
the material becomes "two dimensional" and its DOS become
stair-like, as seen in FIG. 2a. FIG. 2b depicts the DOS of a "one
dimensional" wire with a thickness less than a few tens of
nanometer. Finally, in FIG. 2c when the material reaches the "zero
dimensional" quantum-dot, its density of state becomes discreet
delta functions, similar to atomic or molecular energy levels.
Although in reality the states of a nano-particle are a little
smeared out and look like the dotted lines in FIG. 2d, the DOS
usually is still significantly smaller than the bulk.
[0016] Furthermore, nano-particles can be easily dispersed and
diluted hence it is much easier to observe photo-bleaching. Strong
power dependent absorption has been observed in CdSxSe1-x
nano-particles. As described in the book entitled "Optical
Properties of Semiconductor Nanocrystals" to S. V. Gaponenko,
Cambridge Univ. Press, 1998, Chapter 6.
[0017] Another distinctive feature of semiconductor nano-particle
is the tunabillity of the absorption edge by its size. In a
nano-particle, the electrons and holes are much closer to each
other in this confined space than in bulk. Therefore the Coulomb
interaction between electrons and holes are much stronger than in
the bulk. For optical applications, it is convenient to categorize
the semiconductor nano-particles relative to their bulk exciton
size a.sub.B. If the size of a particle a>a.sub.B, it is in the
weak confinement regime. If a<a.sub.B, then it is in the strong
confinement regime.
[0018] In the weak confinement regime, the nano-particles can still
be treated as bulk materials. The quantization of the electron and
hole energy is much less than the quantization of the exciton
energy levels. Therefore the change in optical properties is mainly
due to the change of exciton energy. A qualitative formula for the
exciton ground state is expressed in equation (1), as described in
an article by Al. L Efros, A. L. Efros, Sov. Phys. Semicon. 1982,
16:772-78.
.omega. = E g - E x + 2 .pi. 2 2 ( m e + m h ) a 2 ( 1 )
##EQU00001##
where E.sub.g is the bulk value for band-gap, E.sub.x is the bulk
value for exciton ground energy, m.sub.e and m.sub.h are the
effective masses of electron and hole respectively, h is the Plank
constant and .omega. is the angular frequency of the photon. It can
be immediately seen from this equation that the absorption peak
energy corresponding to the exciton increases rapidly with size
reduction.
[0019] In the strong confinement case, the nano-particle can not be
treated as bulk materials and the Coulomb interaction can not be
described as a hydrogen-like entity. The energy levels for
electrons and holes no longer form continuous bands. But rather,
they form well separated discreet levels, like in atoms or
molecules. A largely simplified model for absorption spectrum of
nano-particles in the strong confinement regime is described in
equation (2), as described in an article by L. E. Brus, J. Chem.
Phys. 1983, 79:5566-71.
.omega. = E g - 1.8 q 2 .kappa. a + 2 .pi. 2 2 ( m e + m h ) a 2 (
2 ) ##EQU00002##
where E.sub.g is the bulk band-gap, m.sub.e and m.sub.h are the
effective masses of the electron and hole respectively, q is the
electron charge, .kappa. is a constant, h is the Plank constant and
.omega. is the angular frequency of the photon. In equation (2) the
absorption edge again increases rapidly with decreasing size. This
effective band-gap widening effects has been observed in many
materials. As an extreme example, Cd.sub.3P.sub.2, its band-gap
increases from its bulk room temperature value of 0.5 eV to about 2
eV for nano-particles with 2.7 nm diameter.
[0020] There is a variety of ways of manufacturing nano-particles.
An non-exhaustive list includes chemical vapor deposition (CVD),
chemical mechanical polishing (CVP), self-organized growth on
vicinal substrates in various film deposition techniques, laser
ablation, plasma assisted decomposition, sol-gel synthesis,
electro-explosion, and chemical synthesis. Nano-particles with
average particle size as small as <1 nm with different shapes
can be produced. Nano-particles with core in the middle and shell
made of different materials can also be produced. If the standard
deviation of the size distribution of nano-particles is smaller
than 5%, it is called a mono-dispersion. It is also feasible to
manipulate the mono-disperse nano-particles into ordered or
disordered close-packed assemblies possessing very different
properties as their bulk properties. A review of mono-disperse
nano-particles can be found in an article "Synthesis and
Characterization of Monodisperse Nanocrystals and Close-Packed
Nanocyrstal Assemblies", C. B. Murray, C. R. Kagan and M. G.
Bawendi, Annu. Rev. Mater. Sci. 2000, 30:545-610.
[0021] When electrons from inner shells of semiconductor atoms are
excited into the conduction gap, they can absorb lights in the EUV
and soft X-ray spectra. The absorption of inner shell electrons
bleaches in the same manner as those valence band electrons.
Therefore reversible photo-bleachable materials for EUV or soft
X-ray can also be developed based on semiconductor nano-particles
with proper energy levels.
[0022] In summary, advantages of using semiconductor nano-particles
as reversible photo-bleachable materials include: [0023] Most
semiconductors can be fabricated into nano-particles with
relatively low cost. The different band-gap of different
semiconductors can cover from far infrared to ultra-violet. For
example, GaAs can be used for infrared light, AlGaAs and InGaN for
the visible light, and AlGaN and MgZnO for ultra-violet light. Even
for application like 193 nm and 157 nm UV photolithography,
suitable material systems, such as MgZnO, exist. [0024] Easy to
apply. Nano-particles are easy to be formed into thin film or bulk
with different shapes. Thus reduces the overall cost of optical
applications. [0025] The absorption edge of nano-particles can be
tuned by changing their size. This adds another degree of freedom
and simplicity to the design. For example, in the application of UV
photolithography, same CEM can work at 365 nm and 248 nm, even 193
nm, only with different particle size. [0026] Electronic states in
nano-particles are highly localized within the particles. Therefore
an assembly of nano-particles resolve light distribution with high
spatial frequency. [0027] The relaxation time can be manipulated
from pico-second to seconds, provided that certain measures are
taken. It covers time scale required for most optical applications.
An example is shown in Gribkovskii et al, "Optical Nonlinearity of
Semiconductor Microcrystal CdS.sub.xSe.sub.1-x Under the Action of
Picosecond and Nanosecond Laser Pulses", Phys. Stat. Sol. (b) 158:
359-66 (1988), where the surface passivated material relaxed in
less than a nano-second. An example on the other extreme can be
seen in "Organic-Capped ZnO Nanocrystals", M. Shim and Philippe
Guyot-Sionnest, J. Am. Chem. Soc., 2001, 123, 11651. In this
article it is demonstrated that in ZnO nanocrystal relaxation time
varies from minutes to days.
BRIEF DESCRIPTION OF THE DRAWINGS
[0028] These and other features and advantages will be better and
more completely understood by referring to the following detailed
description of presently preferred illustrative embodiments in
conjunction with the drawings, of which:
[0029] FIG. 1 is an exemplary illustration of a prior art contrast
enhancement layer and its effect on a light pattern;
[0030] FIGS. 2a-2c show exemplary illustrative density of states
for various dimensional semiconductor material systems;
[0031] FIG. 3a shows an exemplary illustrative generic light
absorption and recombination process in a semiconductor
nano-particle;
[0032] FIG. 3b shows an exemplary illustrative process removal of a
photo-induced electron or hole from an illustrative nano-particle
to a surrounding solvent;
[0033] FIG. 3c shows an exemplary illustrative process of removal
of a photo-induced electron or hole from an illustrative
nano-particle to an adjacent nano-particle with offset band-gaps;
and
[0034] FIG. 3d shows an exemplary illustrative movement of a
photo-induced electron or hole from one layer of an illustrative
multi-layer nano-particle to another layer of the
nano-particle;
[0035] FIG. 3e shows an exemplary illustrative system of n-type
nano-particles submerged in a p-type polymer matrix;
[0036] FIG. 3f shows an illustrative process where an electron is
ejected via Auger recombination process;
[0037] FIGS. 4a-4d show the use of an exemplary illustrative
reversible contrast enhancement layer in combination with multiple
exposures separated in time and space;
[0038] FIG. 5 shows an exemplary illustrative method of lithography
mask inspecting using a reversible contrast enhancement layer;
[0039] FIG. 6a shows an exemplary illustrative data extracting
mechanism of optical storage device such as compact disc (CD) or
digital versatile disc (DVD). Similar design can also be used for
data recording in a rewritable optical storage device; and
[0040] FIGS. 6b-6d show different exemplary illustrative methods of
incorporating reversible bleachable materials to improve the data
writing density and read resolution;
[0041] FIG. 7a-FIG. 7e show an exemplary illustrative method of
using R-CEL, combined with multiple exposures separated in time and
position created by using a single mask and changing other elements
in the optical system, to increase pattern resolution.
DETAILED DESCRIPTION OF PRESENTLY PREFERRED NON-LIMITING
ILLUSTRATIVE EMBODIMENTS
[0042] One preferred exemplary non-limiting illustrative
embodiments provides a contrast enhancement material comprising
semiconductor nano-sized particles. Said semiconductor may exhibit
a band-gap in its electronic structure; a non-exhaustive list of
said particles may include: C, Si, Ge, CuCl, CuBr, CuI, AgCl, AgBr,
AgI, Ag.sub.2S, CaO, MgO, ZnO, Mg.sub.xZn.sub.1-xO, ZnS, HgS, ZnSe,
CdS, CdSe, CdTe, HgTe, PbS, BN, AlN, GaN, Al.sub.xGa.sub.1-xN, GaP
GaAs, GaSb, InP, InAs, In.sub.xGa.sub.1-xAs, SiC,
Si.sub.1-xGe.sub.x, Si.sub.3N.sub.4, ZrN, CaF.sub.2, YF.sub.3,
Al.sub.2O.sub.3, SiO.sub.2, TiO.sub.2, Cu.sub.2O, Zr.sub.2O.sub.3,
ZrO.sub.2, SnO2, YSi.sub.2, GalnP.sub.2, Cd.sub.3P.sub.2,
Fe.sub.2S, Cu.sub.2S, CuIn.sub.2S.sub.2, MoS.sub.2,
In.sub.2S.sub.3, Bi.sub.2S.sub.3, CuIn.sub.2Se.sub.2,
In.sub.2Se.sub.3, HgI.sub.2, PbI.sub.2 and their various isomers
and alloys; said particles may be in spherical, cubical, rod-like,
tetragonal, single or multi-wall nano-tube or other nano-scale
geometric shapes; and particle may be doped by other elements; said
particles may be coated with one or more shells of other materials;
and said shell material may comprise any known materials.
[0043] Said contrast enhancement material may comprises
nano-particles immersed in polymer matrix and other chemicals; said
contrast enhancement material materials may be spun, sprayed,
rinsed, dipped, evaporated or deposited by any thin film growth
technique, on to a surface to form a reversible photo-bleachable
layer; Said contrast enhancement material may be used in
photolithography at 365 nm, 257 nm 248 nm, 198 nm, 193 nm, 157 nm,
121 nm and other practical wavelengths.
[0044] Another preferred exemplary non-limiting illustrative
embodiments provides a reversible photo-bleachable material
comprising semiconductor nano-sized particles. Said semiconductor
may exhibit a band-gap in its electronic structure; a
non-exhaustive list of said particles may include: C, Si, Ge, CuCl,
CuBr, CuI, AgCl, AgBr, AgI, Ag.sub.2S, CaO, MgO, ZnO,
MgxZn.sub.1-xO, ZnS, HgS, ZnSe, CdS, CdSe, CdTe, HgTe, PbS, BN,
AlN, GaN, Al.sub.xGa.sub.1-xN, GaP GaAs, GaSb, InP, InAs,
In.sub.xGa.sub.1-xAs, SiC, Si.sub.1-xGe.sub.x, Si.sub.3N.sub.4,
ZrN, CaF.sub.2, YF.sub.3, Al.sub.2O.sub.3, SiO.sub.2, TiO.sub.2,
Cu.sub.2O, Zr.sub.2O.sub.3, ZrO.sub.2, SnO.sub.2, YSi.sub.2,
GalnP.sub.2, Cd.sub.3P.sub.2, Fe.sub.2S, Cu.sub.2S,
CuIn.sub.2S.sub.2, MoS.sub.2, In.sub.2S.sub.3, Bi.sub.2S.sub.3,
CuIn.sub.2Se.sub.2, In.sub.2Se.sub.3, HgI.sub.2, PbI.sub.2 and
their various isomers and alloys; said particles may be in
spherical, cubical, rod-like, tetragonal, single or multi-wall
nano-tube or other nano-scale geometric shapes; and particle may be
doped by other elements; said particles may be coated with one or
more shells of other materials; and said shell material may
comprise any known materials.
[0045] Said reversible photo-bleachable material may comprises
nano-particles immersed in polymer matrix and other chemicals; said
reversible photo-bleachable materials may be spun, sprayed, rinsed,
dipped, evaporated or deposited by any thin film growth technique,
on to a surface to form a reversible photo-bleachable layer.
[0046] Upon photon illumination, said reversible photo-bleachable
material may become more transparent to the wavelength of said
photon; said material may become more transparent to wavelength
other than actinic wavelength; said reversible photo-bleachable
material may recover at least part of its original opacity in a
certain period of time after the said illumination is turned off;
said illumination may comprises photon wavelength from far infrared
to deep UV; and said reversible photo-bleachable material may
comprises particles with different compositions and structures.
[0047] Another aspect of preferred exemplary non-limiting
illustrative embodiments of a reversible photo-bleachable material
comprises providing a reversible contrast enhancement (R-CEL) based
on semiconductor nano-particles. Said R-CEL may work in the
spectrum from far-infrared to deep UV in lithography or optical
storage to increase the resolution of the image or storage
density.
[0048] One preferred exemplary non-limiting illustrative
embodiments provides a method to adjust the relaxation of said
nano-particles in said reversible photo-bleachable material
comprises mechanism of separating photon-generated electrons and
holes. As shown in FIG. 3a, in an isolated nano-particle, the
electron-hole pair generated by the light will eventually recombine
in the same particle. A mechanism to increase electrons and holes
lifetime may be to separate said electrons and holes.
[0049] Another aspect of preferred non-limiting illustrative method
of adjusting the relaxation time of said reversible
photo-bleachable material comprises, as shown in FIG. 3b: providing
extra electronic states at the surface of said nano-particles. Said
electronic states may be manipulated to provide adjustable
relaxation time of said reversible photo-bleachable material.
[0050] Said electronic states may function as an electron donor or
acceptor, namely, said electronic states may accept electrons
(acceptor) or holes (donor) when they are generated by actinic
photons; said electronic states may withhold the said electrons or
holes for a certain period of time; said electrons and holes
eventually recombine to allow said nano-particles to recover to at
least part of their original opacity; said electronic states may be
created by the dangling bonds at the said surface; or by capping
said nano-particles with certain chemical surfactants; or by
capping another semiconductor material. An example is that pyridine
can behave as an electron donor when capped onto a CdSe
nano-particle. A review of a prior art can be seen in the article
"Mechanisms for intra-band energy relaxation in semiconductor
quantum dots: The role of electron-hole interactions", V. I.
Klimov, A. A. Mikhailovsky, and D. W. McBranch, Phys. Rev. B. 61,
2000, p.R13349.
[0051] Another aspect of preferred non-limiting illustrative method
of adjusting the relaxation time of said reversible
photo-bleachable material comprises: doping said nano-particles
with transitional metals. Said dopants create trap states in the
nano-particles; said trap states withhold the photo-generated
electrons or holes during and after the exposure; said electrons
and holes eventually recombining to allow said nano-particles
recover to at least part of their original opacity. An example in
the prior art is Fe doped TiO.sub.2 nano-particles as described in
an article by E. C. Butler and A. P. Davis, J. Photochem,
Photobiol., A: Chem. 1993, 70.273.
[0052] Another aspect of preferred non-limiting illustrative method
of adjusting the relaxation time of said reversible
photo-bleachable material comprises: providing surfactant to said
nano-particles. Said surfactant provides electronic states to
withhold photo-generated electrons or holes for a certain period of
time; said electrons and holes eventually recombine to allow said
nano-particles recover to at least part of their original opacity;
said surfactant photo-bleach at the actinic wavelength when
withholding said electrons or holes; said surfactant relax to at
least part of its original opacity when said electrons or holes are
removed from said electronic states.
[0053] Another aspect of preferred non-limiting illustrative method
of adjusting the relaxation time of said reversible
photo-bleachable material comprises, as shown in FIG. 3c: providing
a mixture of two types of nano-particles. The band-gaps of the two
said types of nano-particles are offset relative to each other;
photo-generated electrons or holes are separated due to said offset
of said band-gaps; said electrons and holes eventually recombine to
allow said nano-particles recover to at least part of their
original opacity. For simplicity, FIG. 3c only shows that electrons
are removed under the given illustrative band structure.
[0054] Another aspect of preferred non-limiting illustrative method
of adjusting the relaxation time of said reversible
photo-bleachable material comprises, as shown in FIG. 3d: providing
said nano-particles with a shell including another type of
semiconductor (this type of particle is called "composite
nano-particles"). Band-gap of said shell semiconductor has offsets
relative to the core semiconductor; photo-generated electrons or
holes are separated due to said offset of said band-gaps; said
electrons and holes eventually recombine to allow said
nano-particles recover to at least part of their original opacity.
For simplicity, FIG. 3d only shows that electrons are removed under
the given illustrative band structure. A brief review on composite
nano-particle prior art can be found in the article "Structure and
Photophysics of Semiconductor Nanocrystals", A. Eychmuller, J.
Phys. Chem. B 2000, 104, 6514-6528.
[0055] Another aspect of preferred non-limiting illustrative method
of adjusting the relaxation time of said reversible
photo-bleachable material comprises doped nano-particles and
polymer matrix. As shown in FIG. 3e, an n-type nano-particle is
submerged in a p-type polymer matrix. A built-in electrical field
is therefore established at the interface. Here n-type is defined
as semiconductor with excess electrons at the bottom of the
conduction band. While p-type is defined as semiconductor with
excess holes at the top of the valence band. Photo-generated
electrons or holes are separated due to said offset of said built
field; said electrons and holes eventually recombine to allow said
nano-particles recover to at least part of their original opacity.
P-type nano-particles submerged in an n-type polymer works in a
similar fashion.
[0056] Another aspect of preferred non-limiting illustrative method
of adjusting the relaxation time of said reversible
photo-bleachable material is that even without n or p type
character of the surroundings chemicals, due the difference of work
functions, doped nano-crystals will have a built-in field at the
surface. The exact direction of the field is determined by the
relative Fermi levels of the nano-crystal and the surrounding
chemicals. For n-type nano-particles, to prolong the relaxation
time, the initial Fermi-level of the surrounding chemical should be
lower; for p-type nano-particle, higher.
[0057] Another aspect of preferred non-limiting illustrative method
of adjusting the relaxation time of said reversible
photo-bleachable material comprise, nano-particles; a p-type or
n-type or undoped polymer matrix; Photo-generated electrons or
holes undergoing Auger recombination in nano-particles, electrons
or holes being ejected out and left the particles charged; charged
particles becoming transparent to actinic wavelength due to Quantum
confined Stark Effect; said charged nano-particles being
neutralized to allow said nano-particles recover to at least part
of their original opacity.
[0058] As shown in FIG. 3f, Auger recombination is a radiation-less
process where an electron-hole pair or many electron-hole pairs
recombine and transfer their energy to another carrier. This
carrier therefore could gain enough energy to be ejected out of the
particle. Therefore the particle is ionized and further absorption
is suppressed, due to quantum confined Stark effect, until the
particle is neutralized again. This process manifested itself as
random "blinking" in the nano-crystal photoluminescence, as
described in an article: "Quantum-Confined Stark Effect in Single
CdSe Nanocrystallite Quantum Dots", S. A. Empedocles and M. G.
Bawendi, Science, 1997, 278, p 2114. To modify the relaxation time,
we only have to cap or mix the nanocrystals with donor or acceptor
chemicals so that the generated carriers can be withheld for the
desired period of time.
[0059] Another preferred exemplary non-limiting illustrative
embodiment provides method of exposing a wafer comprising: A
substrate, structured or non-structured; having a layer of
photo-resist thereon; a photon illuminating; providing a contrast
enhancement layer containing semiconductor nano-particles; a mask;
passing said illuminating through said mask to create pattern on
said CEL; and said light pattern bleaches said CEL and expose at
least part of said photo-resist.
[0060] Another preferred exemplary non-limiting illustrative
embodiment provides method of exposing a wafer comprising: A
substrate, structured or non-structured; having a layer of
photo-resist thereon; a pulsed photon illuminating; providing a
R-CEL containing semiconductor nano-particles; a mask; passing said
illuminating through said mask to create pattern on said R-CEL; and
said light pattern bleaches said R-CEL and expose at least part of
said photo-resist.
[0061] Another aspect of preferred non-limiting illustrative method
of exposing a substrate having a photo-resist thereon comprises
providing a R-CEL on said substrate, as shown in FIG. 4a; passing
one said pulse or multiple said pulses of said illuminating through
at least part of said mask to create pattern on said R-CEL, as
shown in FIG. 4b; relaxing said R-CEL, as shown in FIG. 4c; passing
one said pulse or multiple said pulses of said illuminating through
at least part of said mask to create another pattern on said R-CEL,
as shown in FIG. 4d; and said R-CEL bleaches in response to said
illuminating in both exposures. As evidently shown in these
figures, this method could create smaller features and pitches than
the optical diffraction limits would allow. It also can create
smaller pitches than the non-reversible contrast enhancement layer
would allow.
[0062] Another aspect of preferred non-limiting illustrative method
of exposing a substrate having a photo-resist thereon comprises
providing R-CEL on said substrate; providing multiple exposures
separated by time; each said exposure comprising one said pulse or
multiple said pulses of said illuminating through at least part of
said mask to create a pattern on said R-CEL; said R-CEL bleaches in
response to said illuminating in all said exposures; and said
separations of time are long enough to relax said R-CEL.
[0063] Another aspect of preferred non-limiting illustrative method
of exposing a substrate having a photo-resist thereon comprises
providing an R-CEL on said substrate, a second mask having an
arrangement of light areas, i.e. squares, is placed in the optical
path. The second said mask prevents certain parts of the pattern
from the first mask from forming image on the resist during one
exposure. The wafer stage moves the wafer and the second mask
relative to the first mask. In the second exposure, the second mask
prevents certain parts of the pattern from the first mask from
forming image on the resist. The R-CEL is allowed to relax between
exposures. As shown from FIG. 7a to FIG. 7d, this sequence of
movements and exposures can be continued to fill in the final
desired pattern, illustratively shown in FIG. 7e. The arrangement
of light passing and blocking areas in the second mask could take
many forms, including isolated transparent areas, such as squares
or other geometric shapes, a checkerboard of squares or hexagons, a
line of light and dark regions, multiple lines of light and dark
regions, or any other arrangement of some substantially light
passing and some substantially light blocking regions. For the sake
of simplicity, other parts of a lithographic system, such as
demagnification optics, are not shown in FIG. 7.
[0064] Another aspect of preferred non-limiting illustrative method
of exposing a substrate having a photo-resist thereon comprises
providing R-CEL on said substrate; passing one said pulse or
multiple said pulses of said illuminating through one mask to
create a pattern on said R-CEL; relaxing said R-CEL; passing one
said pulse or multiple said pulses of said illuminating through
another mask to create another pattern on said R-CEL; and said
R-CEL bleaches in response to said illuminating in both
exposures.
[0065] Another aspect of preferred non-limiting illustrative method
of exposing a substrate having a photo-resist thereon comprises
providing R-CEL on said substrate; providing multiple exposures
separated by time; each said exposure comprising one said pulse or
multiple said pulses of said illuminating through one mask to
create a pattern on said R-CEL; said R-CEL bleaches in response to
said illuminating in all exposures; and said separations of time
are long enough to relax said R-CEL.
[0066] Another aspect of preferred non-limiting illustrative method
of exposing a substrate having a photo-resist thereon comprises
providing R-CEL on said substrate; a programmable mask; providing
two or multiple exposures separated by time; each said exposure
comprising one said pulse or multiple said pulses of said
illuminating through said mask to create a pattern on said R-CEL;
said R-CEL bleaches in response to said illuminating in all
exposures; said programmable mask maybe re-programmed into another
pattern during said separations of time; said substrate may be
moved relative to said programmable mask during said separation of
time; and said separations of time are long enough to relax said
R-CEL. A detailed description can be found in U.S. Pat. No.
6,291,110 B1, entitled "Methods for Transferring a Two-Dimensional
Programmable Exposure Pattern for Photolithography".
[0067] Another exemplary non-limiting illustrative embodiment
provides a method of resolution enhancement for lithography mask
inspection. The purpose of said inspection is to detect defects or
contamination of said mask. The said method comprises, as shown in
FIG. 5: a mask; a laser beam; an optical objective focuses said
laser beam onto said pattern; providing layer of R-CEL containing
said reversible bleachable material on top of said mask; a detector
or detectors to detect the reflected or transmitted light of said
laser beam; and a mechanism to scan the laser beam across the
entire area of said mask. The mask may comprise a quartz substrate
and a chrome pattern. By applying a R-CEL, the resolution of the
mask inspector is improved.
[0068] Another exemplary non-limiting illustrative embodiment
provides a method of resolution enhancement for lithography mask
writing. The said method comprises: a blank mask; a layer of
photoresist thereon; a said reversible bleachable material
comprising semiconductor nano-particles on top of said photoresist,
a laser beam; an optical system focuses said laser beam onto said
photoresist; and a mechanism to scan the laser beam across the
entire area of said mask to expose said resist. The mask may
comprise a quartz substrate and a chrome layer. The minimal feature
written depends on the focused spot by said objective, which is
close to the diffraction limit. By applying a R-CEL, the size of
the focused light spot may be greatly reduced by trimming off the
less intensive part. Therefore improve the resolution of the
inspection tool.
[0069] Another preferred exemplary non-limiting illustrative
embodiment provides an optical storage device, similar to compact
disc (CD) or digital versatile disk (DVD). As shown in FIG. 6a. In
a typical CD or DVD, the data is stored by pitches on a clear
substrate, usually made of polycarbonate. The substrate is coated
with reflective metal so the reading laser beam can be reflected.
The minimum pitch that can be read by the system is determined by
the focused spot size, which is determined by the diffraction
limit. By applying a R-CEL between the reflecting metal and the
pitches, as depicted in FIG. 6b, the focused spot can be greatly
reduced. This therefore increases the minimum pitch that can be
read that in turn leads to increased storage capacity of each
individual disc.
[0070] The said preferred exemplary non-limiting illustrative
embodiment comprises, as shown in FIG. 6b: a substrate having
information-bearing indicia thereon, and a R-CEL disposed on at
least part of information bearing side of said substrate, a
reflecting metal disposed after the said reversible
photo-bleachable layer, a laser beam; an optical objective focuses
said laser beam onto the said pattern; a detector or detectors to
detect the reflected or transmitted light of said laser beam; and a
mechanism to scan the laser beam across the entire area of said
mask. The R-CEL may contain nano-particles. The substrate may
comprise a plastic disk.
[0071] Another aspect of preferred exemplary non-limiting
illustrative embodiment comprises, as shown in FIG. 6c: a substrate
having information-bearing indicia thereon, and a R-CEL disposed on
at least part of flat side of said substrate, a reflecting metal
disposed on the information bearing indicia, a laser beam; an
optical objective focuses said laser beam onto the said pattern; a
detector or detectors to detect the reflected or transmitted light
of said laser beam; and a mechanism to scan the laser beam across
the entire area of said mask. The R-CEL may contain nano-particles.
The substrate may comprise a plastic disk.
[0072] Another aspect of preferred exemplary non-limiting
illustrative embodiment comprises, as shown in FIG. 6d: a substrate
having information-bearing indicia thereon, a reflecting metal
disposed on the information bearing indicia, a laser beam; an
optical objective focuses said laser beam onto the said pattern; a
detector or detectors to detect the reflected or transmitted light
of said laser beam; and a mechanism to scan the laser beam across
the entire area of said mask. The substrate may comprise mixture of
reversible photo-bleachable material and plastic.
[0073] Another non-limiting aspect may provide an optical storage
device reader or writer comprising: a receptacle adapted to receive
a substrate having optically-scannable information-bearing indicia
and a R-CEL thereon; and a laser scanner arrangement that, in use,
writes and/or scans said information-bearing indicia through said
reversible contrast enhancement layer. The laser scanner
arrangement may be adapted to provide fine positional control to
take advantage of close spacing of said information-bearing indicia
provided by said reversible contrast enhancement layer.
[0074] While the invention has been described in connection with
what is presently considered to be the most practical and preferred
embodiment, it is to be understood that the invention is not to be
limited to the disclosed embodiment, but on the contrary, is
intended to cover various modifications and equivalent arrangements
included within the scope of the appended claims.
* * * * *