Title of Invention

PRINTABLE HOMOGENOUS, PARTICLE-FREE ETCHING MEDIUM

Abstract Printable, homogenous, particle—free etching medium having non-Newtonian flow behaviour for etching inorganic, glass-like or crystalline surfaces such as herein described.
Full Text The present invention relates to novel etching media in the form of printable,'
homogeneous, particle-free etching pastes having non-Newtonian flow
behaviour for etching inorganic, glass-like amorphous or crystalline surfaces,
in particular of glasses or ceramics, preferably on SiO2- or silicon nitride-
based systems, and to the use of these etching media.
The term 'inorganic surfaces' is taken to mean oxidic and nitride-containing
compounds of silicon, in particular silicon oxide and silicon nitride surfaces.
Definition of glass:
The term 'glass' is per se taken to mean a uniform material, for example
quartz glass, window glass or borosilicate glass, and also thin layers of these
materials produced on other substrates (for example ceramics, metal
sheeting or silicon wafers) by various processes known to the person skilled
in the art (CVD, PVD, spin-on, thermal oxidation, inter alia).
The term 'glasses' below is taken to mean silicon oxide- and silicon nitride-
containing materials which exist in the solid amorphous state without the
glass components crystallizing out and have a high degree of disorder in the
microstructure owing to the lack of a long-range order.
Besides pure SiO2 glass (quartz glass), all glasses are included (for example
doped glasses, such as borosilicate, phosphosilicate and borophospho-
silicate glasses, coloured, milk and crystal glasses, optical glasses) which
comprise SiO2 and other components, in particular elements such as, for
example, calcium, sodium, aluminium, lead, lithium, magnesium, barium,
potassium, boron, beryllium, phosphorus, gallium, arsenic, antimony,
lanthenum, zinc, thorium, copper, chromium, manganese, iron, cobalt, nickel,
molybdenum, vanadium, titanium, gold, platinum, palladium, silver, cerium,
caesium, niobium, tantalum, zirconium, neodymium and praseodymium,
which occur in the glasses or function as doping elements in the glasses in
the form of oxides, carbonates, nitrates, phosphates, sulfates and/or halides.
Doped glasses are, for example, borosilicate, phosphosilicate and
borophosphosilicate glasses, coloured, milk and crystal glasses and optical
glasses.
The silicon nitride may likewise comprise other elements, such as boron,
aluminium, gallium, indium, phosphorus, arsenic or antimony.
Definition of silicon oxide- and silicon nitride-based systems:
The term 'silicon oxide-based systems' is applied below to all crystalline
systems which do not fall under the definition given above for amorphous
SiO2 glasses and are based on silicon dioxide; these can be, in particular, the
salts and esters of orthosilicic acid and condensation products thereof-
generally referred to as silicates by the person skilled in the art - and quartz
and glass-ceramics.
This definition also covers other silicon oxide- and silicon nitride-based
systems, in particular the salts and esters of orthosilicic acid and
condensation products thereof. Besides pure SiO2 (quartz, tridymite and
cristobalite), the definition covers all SiO2-based systems that are built up
from SiO2 or from 'discrete' and/or linked [SiO4] tetrahedra, such as, for
example, nesosilicates, sorosilicates, cyclosilicates, inosilicates, phyllo-
silicates and tectosilicates, and other components, in particular elements/
components such as, for example, calcium, sodium, aluminium, lithium,
magnesium, barium, potassium, beryllium, scandium, manganese, iron,
titanium, zirconium, zinc, cerium, yttrium, oxygen, hydroxyl groups and
halides.
The term 'silicon nitride-based systems' is applied below to all crystalline and
partially crystalline (usually referred to as microcrystalline) systems which do
not fall under the definition given above for amorphous silicon nitride
glasses/layers. These include Si3N4 in its a-Si3N4,and ß-Si3N4modifications
and all crystalline and partially crystalline SiNx and SiNx:H layers. The
crystalline silicon nitride may be doped by other elements, such as boron,
aluminium, gallium, indium, phosphorus, arsenic and antimony.
1. Etching of structures on glass
The use of etchants, i.e. chemically aggressive compounds, causes
dissolution of the material subjected to the attack by the etchant. It is not only
the first layer of the attack surface but also - seen from the attack surface -
deeper layers that are attacked and removed.
2. Etching of structures on silicon oxide- and silicon nitride-based glasses and
other silicon oxide- and silicon nitride-based systems
According to the current state of the art, any desired structures can be etched
selectively in silicon oxide- and silicon nitride-based glasses and other silicon
oxide- and silicon nitride-based systems or their surfaces or their layers of
variable thickness, directly by laser-supported etching methods or, after
masking, by wet-chemical methods [1,2] or by dry-etching methods [3].
In the laser-supported etching methods, the laser beam scans the entire etch
pattern point for point on the glass, which, in addition to a high degree of
precision, also requires considerable adjustment effort and is very time-
consuming.
The wet-chemical and dry etching methods include material-intensive, time-
consuming and expensive process steps:
A. masking of the areas not to be etched, for example by:
• photolithography: production of a negative or positive of the etch structure
(depending on the resist), coating of the substrate surface (for example by
spin coating with a suitable photoresist), drying of the photoresist,
exposure of the coated substrate surface, development, rinsing, if desired
drying
B. etching of the structures by:
• dip methods (for example wet etching in wet-chemical banks): dipping of
the substrates into the etch bath, etching process, repeated rinsing in H2O
cascade basins, drying
• spin-on or spray methods: the etching solution is applied to a rotating
substrate, the etching operation can take place without/with input of energy
(for example IR or UV irradiation), and this is followed by rinsing and drying
• dry-etching methods, such as, for example, plasma etching in expensive
vacuum units or etching with reactive gases in flow reactors
[1] D.J. Monk, D.S. Soane, R.T. Howe, Thin Solid Films 232 (1993), 1
[2] J. Bühler, F.-P. Steiner, H. Baltes, J. Micromech. Microeng. 7 (1997), R1
[3] M. Köhler "Ätzverfahren für die Mikrotechnik" [Etching Methods for
Microtechnology], Wiley VCH 1998.
3. Full-area etching of silicon oxide- and silicon nitride-based glasses and
other silicon oxide- and silicon nitride-based systems
In order to etch silicon oxide- and silicon nitride-based glasses and other
silicon oxide- and silicon nitride-based systems and their layers of variable
thickness to a certain depth over the entire area, use is predominantly made
of wet-etching methods. The silicon oxide- and silicon nitride-based glasses
and other silicon oxide- and silicon nitride-based systems and their layers of
variable thickness are dipped into etch baths, which usually contain toxic and
highly corrosive hydrofluoric acid or another mineral acid as etching
component.
The disadvantages of the etching methods described are due to the time-
consuming, material-intensive, expensive process steps which are in some
cases complex from a technologically or safety point of view or are carried
out batchwise.
The object of the present invention is therefore to provide an etching medium
which can be employed in a technologically simple etching method with high
potential throughputs for inorganic surfaces, in particular for glass and other
silicon oxide- or silicon nitride-based systems, and their layers of variable
thickness, this simple etching method being significantly less expensive than
conventional wet and dry etching methods in the liquid or gas phase.
The invention thus relates to printable, homogeneous, particle-free etching
pastes which have an advantageous, non-Newtonian flow behaviour, and to
the use thereof for etching inorganic surfaces, in particular surfaces of silicon
oxide- and silicon nitride-based glasses and other silicon oxide- and silicon
nitride-based systems and their layers of variable thickness.
The invention also relates to the use of these homogeneous, particle-free
etching pastes which have non-Newtonian flow behaviour in - compared with
the conventional wet and dry etching methods in the liquid or gas phase -
less expensive, technologically simple printing/etching methods for glass and
for other silicon dioxide- and silicon nitride-based systems which are suitable
for high throughputs and can be carried out continuously.
The production, shaping and aftertreatment, such as, for example, grinding,
polishing, lapping and heat treatment, of the SiO2-based systems are - as in
the case of the glasses - unimportant for the use described in accordance
with the invention of printable, homogeneous, particle-free etching pastes
having non-Newtonian flow behaviour.
The invention relates both to the etching of SiO2- or silicon nitride-coated
substrates as uniform, full, nonporous and porous solids (for example glass
grains and powders, and flat, hollow, mirror or sintered glass), obtained, for
example, from glass melts, and also to the etching of nonporous and porous
glass layers of variable thickness which have been produced on other
substrates (for example on ceramics, metal sheeting or silicon wafers) by
various methods known to the person skilled in the art (for example CVD,
PVD, spin-on of Si-containing precursors, thermal oxidation ...).
The etching pastes are applied in a single process step to the substrate
surface to be etche.d. The surface to be etched can be a surface or part-
surface on a homogeneous, solid, porous or nonporous element made from
silicon oxide- or silicon nitride-based glass or other silicon oxide- or silicon
nitride-based systems (for example the surface of a silicon oxide glass sheet)
and/or a surface or part-surface of a porous or nonporous layer of glass or
other silicon oxide- or silicon-nitride based systems on a support material.
A method with a high degree of automation and high throughput which is
suitable for transfer of the etching paste to the substrate surface to be etched
uses printing technology. In particular, screen printing, silk-screen printing,
pad printing, stamp printing and ink-Jet printing methods are printing methods
which are known to the person skilled in the art. Manual application is
likewise possible.
Depending on the design of the screen, silk screen, klischee or stamp or the
cartridge addressing, it is possible to apply the printable, homogeneous,
particle-free etching pastes having non-Newtonian flow behaviour which are
described in accordance with the invention over the entire area or selectively
in accordance with the etch structure mask only to the points at which etching
is desired. All masking and lithography steps as described under A) are
unnecessary. The etching operation can take place with or without input of
energy, for example in the form of heat radiation (using IR emitters). After
etching is complete, the printable, homogeneous, particle-free etching pastes
having non-Newtonian flow behaviour are rinsed off the etched surface using
a suitable solvent or burnt out.
By variation of the following parameters, the etch depth in silicon oxide- and
silicon nitride-based glasses or other silicon oxide- and silicon nitride-based
systems and their layers of variable thickness, and in the case of selective
structure etching, in addition the edge sharpness of the etch structures can
be adjusted;
• concentration and composition of the etching components
• concentration and composition of the solvents employed
• concentration and composition of the thickener systems
• concentration and composition of any acids added
• concentration and composition of any additives added, such as antifoams,
thixotropic agents, flow-control agents, deaeration agents and adhesion
promoters
• viscosity of the printable, homogeneous, particle-free etching pastes
having non-Newtonian flow behaviour which are described in accordance
with the invention
• etching duration with or without input of energy into the inorganic surfaces
printed with the respective printing paste and their layers, and
• input of energy into the system printed with the etching paste.
The etching duration can be between a few seconds and several minutes,
depending on the application, desired etching depth and/or edge sharpness
of the etch structures. In general, an etching duration of between 1 and 15
minutes is set.
The printable, homogeneous, particle-free etching pastes having non-
Newtonian flow behaviour which are described in accordance with the
invention are - compared with liquid, dissolved or gaseous etchants, such as
inorganic mineral acids from the group consisting of hydrofluoric acid,
fluorides, HF gas and SF6 - advantageously significantly simpler and safer to
handle and are significantly more economical with respect to the amount of
etchant.
The printable, homogeneous, particle-free etching pastes having non-
Newtonian flow behaviour according to the invention have the following
composition:
a. an etching component for glass or for other SiO2-based systems and
layers thereof
b. solvent
c. thickener
d. if desired, organic and/or inorganic acid(s)
e. if desired, additives, such as antifoams, thixotropic agents, flow-control
agents, deaeration agents and adhesion promoters.
The etching action of the printable, homogeneous, particle-free etching
pastes having non-Newtonian flow behaviour which are described in
accordance with the invention on surfaces of silicon oxide- and silicon nitride-
based glasses and other silicon oxide- and silicon nitride-based systems is
based on the use of solutions of fluoride-containing components with or
without addition of acid, in particular solutions of fluorides, bifluorides,
tetrafluoroborates, such as, for example, ammonium, alkali metal and
antimony fluorides, ammonium, alkali metal and calcium bifluorides, alkylated
ammonium and potassium tetrafluoroborates, and mixtures thereof. These
etching components are effective in the etching pastes even at temperatures
in the range from 15 to 50°C, in particular at room temperature, and/or are
activated by input of energy, for example by thermal radiation by IR emitters
(up to about 300°C), UV or laser radiation.
The proportion of the etching components employed is in a concentration
range of from 2 to 20% by weight, preferably in the range from 5 to 15% by
weight, based on the total weight of the etching paste.
The solvent may form the principal constituent of the etching paste. The
proportion can be in the range from 10 to 90% by weight, preferably in the
range from 15 to 85% by weight, based on the total weight of the etching
paste.
Suitable solvents may be inorganic and/or organic solvents, or mixtures
thereof. Suitable solvents, which can be employed in pure form or in
corresponding mixtures, may be, depending on the application:
• water
• simple or polyhydric alcohols, such as, for example, diethylene glycol,
dipropylene glycol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol,
glycerol, 1,5-pentanediol, 2-ethyl-1-hexanol, or mixtures thereof,
• ketones, such as, for example, acetophenone, methyl-2-hexanone, 2-
octanone, 4-hydroxy-4-methyl-2-pentanone or 1-methyl-2-pyrrolidone
• ethers, such as ethylene glycol monobutyl ether, triethylene glycol
monomethyl ether, diethylene glycol monobutyl ether or dipropylene glycol
monomethyl ether
• carboxylic acid esters, such as [2,2-butoxy(ethoxy)]ethyl acetate
• esters of carbonic acid, such as propylene carbonate
• inorganic mineral acids, such as hydrochloric acid, phosphoric acid,
sulfuric acid or nitric acid, or organic acids which have an alkyl radical
chain length of n = 1 -10, or mixtures thereof. The alkyl radical may be
either straight-chain or branched. In particular, organic carboxylic, hydroxy-
carboxylic and dicarboxylic acids, such as formic acid, acetic acid, lactic
acid, oxalic acid or the like, are suitable.
These solvents or mixtures thereof are, inter alia, also suitable for removing
the etching medium again after etching is complete and, if desired, cleaning
the etched surface.
The viscosity of the printable, homogeneous, particle-free etching pastes
having non-Newtonian flow behaviour which are described in accordance
with the invention is achieved by network-forming thickeners which swell in
the liquid phase and can be varied depending on the desired area of
application. The printable, homogeneous, particle-free etching pastes having
non-Newtonian flow behaviour which are described in accordance with the
invention include all etching pastes whose viscosity is not independent of the
shear rate, in particular etching pastes having a shear-thinning action. The
network produced by thickeners collapses under shear stress. The
restoration of the network can take place without time delay (non-Newtonian
etching pastes having a plastic or pseudoplastic flow behaviour) or with a
time delay (etching pastes having a thixotropic flow behaviour).
The printable, homogeneous, particle-free etching pastes having non-
Newtonian flow behaviour are completely homogeneous with addition of
thickener. Particulate thickeners, such as, for example, particulate silicone or
acrylic resins, are not used.
Possible thickeners are polymers based on the following monomer units:
• glucose units
- ß-glucosidically linked, i.e. cellulose and/or cellulose derivatives, such
as cellulose ethers, in particular ethyl- (for example Aqualon® EC),
hydroxylpropyl- (for example Klucel®) and hydroxyethylcellulose (for
example Natrosol®), and salts of the glycol acid ether of cellulose, in
particular sodium carboxymethylhydroxyethylcellulose (for example Na-
CMHEC)
- a-glucosidically linked, i.e. starch and/or starch derivatives, such as
oxidized starch, in particular sodium carboxymethylstarch (vivastar®
P0100 or vivastar® P5000), and starch ethers, in particular anionic
heteropolysaccharides (Deuteron® VT819 or Deuteron® XG)
• functionalized methacrylate units, in particular cationic
methacrylate/methacrylamide, such as Borchigel® A PK
• functionalized vinyl units, i.e.
- polyvinyl alcohols of various degree of hydrolysis, in particular Mowiol®
47-88 (partially hydrolysed, i.e. vinyl acetate and vinyl alcohol units) or
Mowiol® 56-98 (fully hydrolysed)
- polyvinylpyrolidones (PVP), in particular PVP K-90 or PVP K-120
The thickeners can be employed individually or in combinations with other
thickeners.
The proportion of the thickeners that is necessary for specific setting of the
viscosity range and basically for the formation of a printable paste is in the
range from 0.5 to 25% by weight, preferably from 3 to 20% by weight, based
on the total weight of the etching paste.
As already described, the etching pastes according to the invention are also
completely homogeneous with addition of thickener. They do not comprise
any particulate thickeners, such as, for example, particulate silicone or acrylic
resins.
Organic and inorganic acids whose pKa value is between 0 and 5 may have
been added to the printable, homogeneous, particle-free etching pastes
having non-Newtonian flow behaviour which are described in accordance
with the invention. Inorganic mineral acids, such as, for example, hydrochloric
acid, phosphoric acid, sulfuric acid and nitric acid, and also organic acids
which have an alkyl radical chain length of n = 1 -10 improve the etching
action of the printable, homogeneous, particle-free etching pastes having
non-Newtonian flow behaviour. The alkyl radical of the organic acids may be
either straight-chain or branched, with organic carboxylic, hydroxycarboxylic
and dicarboxylic acids, such as formic acid, acetic acid, lactic acid and oxalic
acid, or others being particularly suitable. The proportion of the acid(s) can be
in the range from 0 to 80% by weight, based on the total weight of the etching
paste.
Additives having properties which are advantageous for the desired purpose
are
antifoams, such as, for example, the one available under the trade name
TEGO® Foamex N,
thixotropic agents, such as BYK® 410, Borchigel® Thixo2,
flow-control agents, such as TEGO® Glide ZG 400,
deaeration agents, such as TEGO® Airex 985, and
adhesion promoters, such as Bayowet® FT 929.
These may have a positive effect on the printability of the printing paste. The
proportion of the additives is in the range from 0 to 5% by weight, based on
the total weight of the etching paste.
Areas of application for the etching pastes according to the invention are
found, for example, in
• the solar cell industry (photovoltaic components, such as solar cells and
photodiodes)
• the semiconductor industry
• the glass industry
• high-performance electronics
The novel printable, homogeneous, particle-free etching pastes having non-
Newtonian behaviour according to the invention can be employed, in
particular, in all cases where full-area and/or structured etching of surfaces of
silicon oxide- and silicon nitride-based glasses and other silicon oxide- and
silicon nitride-based systems and their layers is desired.
Thus, entire surfaces, but also individual structures selectively can be etched
down to the desired depth into uniform, solid, nonporous and porous glasses
and other uniform, solid, nonporous and porous silicon oxide- and silicon
nitride-based systems, i.e. the etching operation can cover all ranges
between microstructural roughening (still transparent glasses with a light-
scattering effect) via frosting/matting effects to etching of deep etch
structures (for example markings, ornaments/patterns). Areas of application
are, for example:
• the production of viewing windows for valves and measuring equipment of
all types
• the production of glass supports for outdoor applications (for example for
solar cells and heat collectors)
• etched glass surfaces in the medical and sanitary sector, and for
decorative purposes, including artistic and architectural applications
• etched glass containers for cosmetic articles, foods and drinks
• specific partial etching of glasses and other silicon oxide-based systems
for marking and labelling purposes, for example for marking/labelling
container glass and flat glass
• specific partial etching of glasses and other silicon oxide-based systems
for mineralogical, geological and microstructural studies
In particular, screen printing, silk-screen printing, pad printing, stamp printing
and ink-jet printing methods are suitable techniques for applying the etching
pastes as desired. In general, besides the said printing methods, manual
application (for example brush) is also possible.
Besides industrial application, the etching pastes are also suitable for DIY
and hobby needs.
The printable, homogeneous, particle-free etching pastes having non-
Newtonian flow behaviour which are described in accordance with the
invention can be employed in all cases where layers of glasses and other
silicon oxide-based and silicon nitride-based systems of variable thickness
are to be etched over the entire area and/or in a structured manner. Areas of
application are, for example:
• all etching steps on layers of silicon oxide- and silicon nitride-based
glasses and other silicon oxide- and silicon nitride-based systems which
result in the production of photovoltaic components, such as solar cells,
photodiodes and the like, in particular
a) the removal of silicon oxide/doped silicon oxide (for example
phosphorus glass after n-doping of the solar cell) and silicon nitride
layers
b) the selective opening of passivation layers of silicon oxide and silicon
nitride for the generation of two-stage selective emitters (after opening,
re-doping in order to produce n+ + layers) and/or local p+ back surface
fields (BSFs)
c) edge etching of silicon oxide- and/or silicon nitride-coated solar-cell
panels
• all etching steps on layers of silicon oxide- and silicon nitride-based
glasses and other silicon oxide- and silicon nitride-based systems which
result in the production of semiconductor components and circuits and
which require the opening of passivation layers of silicon oxide and silicon
nitride
• all etching steps on layers of silicon oxide- and silicon nitride-based
glasses and other silicon oxide- and silicon nitride-based systems which
result in the production of components in high-performance electronics
In particular, screen printing, silk-screen printing, pad printing, stamp printing
and ink-jet printing methods are suitable techniques for application of the
etching pastes as desired. In general, besides the said printing methods,
manual application is also possible.
Besides industrial application, the etching pastes are also suitable for DIY
and hobby needs.
Examples
For better understanding and for illustration, examples are given below which
are within the scope of protection of the present invention, but are not
suitable for restricting the invention to these examples.
Example 1
21 g of ethylene glycol monobutyl ether
39 g of 35% NH4HF2 solution
30 g of formic acid (98-100%)
10 g of PVP K-120
Ethylene glycol monobutyl ether and formic acid are introduced into a PE
beaker. An aqueous 35% NH4HF2 solution is then added. PVP K-120 is then
added successively with stirring (at least 400 rpm). During the addition and
for about 30 minutes thereafter, vigorous stirring must be continued. The
transfer into containers takes place after a short standing time. This standing
time is necessary so that the bubbles formed in the etching paste are able to
dissolve.
This mixture gives an etching paste with which silicon oxide- and silicon
nitride-based glasses and other silicon oxide- and silicon nitride-based
systems and their layers can be etched specifically down to the desired depth
over the entire area or in structures with and/or without input of energy.
The etching rate, determined by photospectrometry, on a thermally generated
silicon oxide layer is 120 nm/min in the case of etching over the entire area.
The etching rate, determined by photospectrometry, on a silicon nitride layer
generated by means of PE-CVD (refractive index n = 1.98) is 70 nm/min in
the case of etching over the entire area.
The etching paste obtained has a long shelf life, is easy to handle and is
printable. It can be removed from the printed material or from the paste
carrier (screen, knife, silk screen, stamp, klischee, cartridge, etc.), for
example, using water, or burnt out in an oven.
Example 2
22 g of triethylene glycol monomethyl ether
43 g of 35% NH4HF2 solution
20 g of demineralized water
12 g of PVP K-120
Triethylene glycol monomethyl ether is initially introduced, and all the liquid
components are added with stirring as in Example 1. Finally, the thickener
PVP K-120 is introduced successively with stirring (at least 400 rpm). During
the addition and for about 30 minutes thereafter, vigorous stirring must be
continued. The transfer into containers takes place after a short standing
time. This standing time is necessary in order that the bubbles formed in the
etching paste are able to dissolve.
This mixture gives an etching paste with which silicon oxide- and silicon
nitride-based glasses and other SiO2- and silicon nitride-based systems and
their layers can be etched specifically down to the desired depth over the
entire area or in structures with and/or without input of energy.
The etching rate, determined by photospectrometry, on a thermally generated
silicon oxide layer is 106 nm/min in the case of etching over the entire area.
The etching paste obtained has a long shelf life, is easy to handle and is
printable. It can be removed from the printed material or from the paste
carrier (screen, knife, silk screen, stamp, klischee, cartridge, etc.), for
example, using water or burnt out in an oven.
Example 3
12 g of solid NH4HF2
142 g of lactic acid
10 g of ethylcellulose
36 g of ethylene glycol monobutyl ether
The ethylcellulose is stirred successively into the initially introduced ethylene
glycol monobutyl ether at 40°C in a water bath. The solid NH4HF2 is dissolved
in the lactic acid, likewise with stirring, and subsequently added to the
ethylcellulose stock paste. The two together are then stirred at 600 rpm for 2
hours.
This mixture gives an etching paste with which silicon oxide- and silicon
nitride-based glasses and other silicon oxide- and silicon nitride-based
systems and their layers can be etched specifically down to the desired depth
over the entire area or in structures with and/or without input of energy.
The etching rate, determined by photospectrometry, on a thermally generated
silicon oxide layer is 23 nm/min in the case of etching over the entire area.
The etching paste obtained has a long shelf life, is easy to handle and is
printable. It can be removed from the printed material or from the paste
carrier (screen, knife, silk screen, stamp, klischee, cartridge, etc.), for
example, using acetone or butyl acetate or burnt out in an oven.
Example 4
15 g of ethylene glycol monobutyl ether
15 g of triethylene glycol monomethyl ether
29 g of propylene carbonate
72 g of formic acid
46 g of 35% NH4HF2 solution
24 g of PVP K-90
The solvent mixture and the formic acid are introduced into a PE beaker. An
aqueous 35% NH4HF2 solution is then added. PVP K-120 is then added
successively with stirring (at least 400 rpm). During the addition and for about
30 minutes thereafter, vigourous stirring must be continued. The transfer into
containers takes place after a short standing time. This standing time is
necessary so that the bubbles formed in the etching paste are able to
dissolve.
This mixture gives an etching paste with which silicon oxide- and silicon
nitride-based glasses and other silicon oxide- and silicon nitride-based
systems and their layers can be etched specifically down to the desired depth
over the entire area or in structures with and/or without input of energy.
The etching rate, determined by photospectrometry, on a thermally generated
silicon oxide layer is 67 nm/min in the case of selective etching of structures
with a width of about 80 µm. The etching rate, determined by photo-
spectrometry, on a silicon nitride layer generated by means of PE-CVD is
35 nm/min in the case of selective etching of structures with a width of about
100 µm and at an etching temperature of 40°C.
The etching paste obtained has a long shelf life, is easy to handle and is
printable. It can be removed from the printed material or from the paste
carrier (screen, knife, silk screen, stamp, klischee, cartridge, etc.), for
example, using water, or burnt out in an oven.
WE CLAIM:
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1. Printable, homogenous, particle-free etching medium having
non-Newtonian flow behaviour for etching inorganic, glass-like or
crystallin surfaces, such as herein described.
2. Printable etching meidum as claimed in claim 1 for
surfaces of glasses selected from the group consisting of the
glasses based on silicon oxide and the glasses based on silicon
nitride.
3. Printable etching medium as claimed in claims 1 and 2, for
surfaces of glasses comprising elements selected from the group
consisting of calcium, sodium, aluminiumt lead, lithium,
magesiums, barium, potassium, boron, beryllium, phosphorus,
gallium, arsenic, antimony, lanthanum, scandium, zinc, thorium,
capper, chromium, manganese, iron cobalt, nickel, molybdenum,
vanadium, titanium, gold, platinum, palladium, silver, cerium,
caesium, niobium, tantalum, zirconium, yttrium, neodymium and
praseodymium.
4. Printable etching medium as claimed in claims 1 to 3
wherein it is an etching paste having non-Newtonian flow
behaviour.
3. Printable itching medium as claimed in claims 1 to 4
wherein it is a homogeneous, particle—free etching paste which
comprises:
a) at least one etching component for inorganic surfaces
such as herein described, in a concentration of from 2 to 20% by
weight;
b) solvent such as herein described in an amount 10 to 90%
by wt;
c) thickener such as herein described in an amount of from
0.3 to 23X by weight;
d) if desired, organic and/or inorganic acid, and, if
desired,
e) additives, such as antifoams, thixotropic agents, flow-
control agents, deaeration agents and adhesion promoters,
is effective even at temperatures of from 13 to 50 C or is
activated, if necessary, by input of energy.
6. Etching medium as claimed in claim 5, wherein it comprises
as etching component, at least one compound selected from the
group consisting of the fluorides, bifluorides and tetrafluoro-
borates and, if desired, at least one inorganic and/or organic
acid such as herein described, where the etching component(s) is
(are) preferably present in a concentation of from 5 to 15% by
weight, based on the total amount.
7. Etching medium as claimed in claim 5 and 6, wherein it
comprises, as etching component,
at least one fluorine compound selected from the group
consisting of the ammonium, alkali metal and antimony fluorides,
ammonium, alkali metal and calcium bifluorides, and alkylated
ammonium and potassium tetrafluoroborates and if desired, at
least one inorganic mineral acid selected from the group
consisting of hydrochloric acidt phosphoric acid, sulfuric acid
and nitric acid and/or, if desired, at least one organic acid,
which may contain a straight-chain or branched alkyl radical
having 1-10 carbon atoms* selected from the group consisting of
alkylcarboxylic acids hydroxycarboxylic acids and dicarboxylic
acids.
8. Etching medium as claimed in claim 5 wherein it comprise
an organic acid selected from the group consisting of formic acid
acetic acid, lactic acid and oxalic acid.
9. Etching medium as claimed in claims 9 to 8 wherein the
proportion of the organic and/or inorganic acids is in a concen-
tration range from 0 to 80X by weight, based on the total amount
of the medium, the added acids each having a pK value of bitween
0 and 9.
10. Etching medium as claimed in claim 5 wherein it
comprises, a solvent, water, monohydric or polyhydric alcohols,
such as glycerol, 1,2-propanediol, 1-4-butanediol, 1,3-
butanediol, 1-5-pentanediol, 2-ehtyl-1-hexenol, ethylene glycol,
diethylene glycol and dipropylene glycol, and ethers therof,
such as ethylene glycol monobutyl ether, triethylene glycol mono-
methyl ether, diethylene glycol monobutyl ether and dipropylene
glycol monomethyl ether, and esters such as (2,2-butoxy(ethoxy)]
ethyl acetate esters of carbonic acid, such as propylene
carbonate, ketones such as acetophenone, methyl-2-hexanone, 2—
octanone, 4-hydroxy-4-methyl-2-pentanone and 1-methyl-2-pyrroli-
done, as such or as a mixture preferably in an amount of from 15
to 85% by weight, based on the total amount of the medium.
11. Etching medium as claimed in claim 5 wherein it comprises
preferably from 3 to 20% by weight, based on the total amount of
the etching medium, of, as thickener, cellulose/cellulose
derivatives, starch/starch derivatives and/or polymers based on
acrylate or functionalized vinyl units.
12. Etching medium as claimed in claim 5 wherein it comprises
from 0 to 5% by weight, based on the total amount of additives
selected from the group consisting of antifoams, thixotropic
agents, flow-control agents, deaeration agents and adhesion
promoters such as herein described.
13. Method for etching inorganic, glass-like,crystall-
ine surfaces, wherein an etching medium as claimed in claim 1-12
is applied over the entire area or specifically in accordance
with the etch structure mask only to the points at which etching
is desired, and, after etching is complete, is rinsed off with
a solvent or solvent mixture of burnt off in an oven.
14. Method as claimed in claim 13 wherein the etching medium
is rinsed off with water after the etching is complete.
15. The method as claimed in claims 13 and 14, wherein said
etching medium is applied to the surface to be etched and removed
again after an exposure time of 1-15 minutes.
16. The method as claimed in claims 13 and 14 in the photo-
voltaics, semiconductor technology, high-performance electronics,
mineralogy or glass industries and for the production of
photodiodes, of viewing windows for valves or measuring
equipment, of glass supports for outdoor applications, for the
production of etched glass surfaces in the medical, decorative
and sanitary sectors, for the production of etched glass
containers for cosmetic articles, foods and drinks, for the
production of markings or labels or containers and in the
production of flat glass.
17. The method as claimed in claims 13 and 14, in screen
printing, silk-screen printingt pad printing, stamp printing, ink-
jet printing and manual printing methods.
16. Method as claimed in claims 13 and 14 for the production
of glass supports for solar cells or for thermal collectors.
19. Method as claimed in claims 13 and 14 for etching SiO2 -
or silicon nitride-containing glasses as uniforms full nonporous
or porous solids or of corresponding nonporous or porous glass
layers of variable thickness which have been produced on other
substrates.
20. Method as claimed in claims 13 and 14 for etching
uniforms solid, nonporous or porous glasses based on silicon
oxide or silicon nitride systems and of variable-thickness layers
of such systems.
21. Method as claimed in claims 13 and 14 for the removal
of silicon oxide/doped silicon oxid and silicon nitride layers,
for the selective opening of passivation layers of silicon oxide
and silicon nitride for the generation of two- stage selective
emitters and/or local p+ back surface fields and for the edge
etching of silicon oxide-and silicon nitride-coated solar cells.
22. Method as claimed in claims 13 and 14 for opening
passivation layers of silicon oxide and silicon nitride in the
process for the production of semiconductor components and their
circuits.
23. Method as claimed in claims 13 and 14 for opening
passivation layers of silicon oxide and silicon nitride in the
process for the production of components for high—performance
electronics.
24. Method as claimed in claims 13 and 14 for mineralogical
geological and microstructural studies.
Printable, homogenous, particle—free etching medium having
non-Newtonian flow behaviour for etching inorganic, glass-like or
crystalline surfaces such as herein described.

Documents:

IN-PCT-2002-1441-KOL-FORM-27.pdf

in-pct-2002-1441-kol-granted-abstract.pdf

in-pct-2002-1441-kol-granted-claims.pdf

in-pct-2002-1441-kol-granted-correspondence.pdf

in-pct-2002-1441-kol-granted-description (complete).pdf

in-pct-2002-1441-kol-granted-examination report.pdf

in-pct-2002-1441-kol-granted-form 1.pdf

in-pct-2002-1441-kol-granted-form 18.pdf

in-pct-2002-1441-kol-granted-form 2.pdf

in-pct-2002-1441-kol-granted-form 3.pdf

in-pct-2002-1441-kol-granted-form 5.pdf

in-pct-2002-1441-kol-granted-gpa.pdf

in-pct-2002-1441-kol-granted-priority document.pdf

in-pct-2002-1441-kol-granted-reply to examination report.pdf

in-pct-2002-1441-kol-granted-specification.pdf

in-pct-2002-1441-kol-granted-translated copy of priority document.pdf


Patent Number 225482
Indian Patent Application Number IN/PCT/2002/1441/KOL
PG Journal Number 46/2008
Publication Date 14-Nov-2008
Grant Date 12-Nov-2008
Date of Filing 25-Nov-2002
Name of Patentee MERCK PATENT GMBH
Applicant Address FRANKFURTER STRASSE 250, 64293 DARMSTADT
Inventors:
# Inventor's Name Inventor's Address
1 KLEIN, SYLKE AUF DEM WINGERT 8, 64380 ROSSDORF
2 HEIDER LILIA LAGERSTRASSE 37A, 64560 RIEDSTADT
3 ZIELINSKI, CLAUDIA STORMSTRASSE 15, 64291 DARMSTADT
4 KUBELBECK, ARMIN AUGARTENSTRASSE 45, 64625 BENSHEIM
5 STOCKUM, WERNER WALDSTRASSE 59, 64354 REINHEIM
PCT International Classification Number C03C 15/00
PCT International Application Number PCT/EP01/03317
PCT International Filing date 2001-03-23
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 101 01 926.2 2001-01-16 Germany
2 100 20 817.7 2000-04-28 Germany