CA1061159A - Method of etching a pattern in glass - Google Patents
Method of etching a pattern in glassInfo
- Publication number
- CA1061159A CA1061159A CA235,541A CA235541A CA1061159A CA 1061159 A CA1061159 A CA 1061159A CA 235541 A CA235541 A CA 235541A CA 1061159 A CA1061159 A CA 1061159A
- Authority
- CA
- Canada
- Prior art keywords
- glass
- pyrolysable
- etching
- layer
- pattern
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
ABSTRACT:
In order to coat glass with a satisfactorily adhering photosensitive etching resist for the purpose of etching patterns in the glass, first an uniform TiO2 layer is deposited by bringing the glass surface into contact with a pyrolysable titanium compound at a tem-perature between 180 °C and 240 °C.
In order to coat glass with a satisfactorily adhering photosensitive etching resist for the purpose of etching patterns in the glass, first an uniform TiO2 layer is deposited by bringing the glass surface into contact with a pyrolysable titanium compound at a tem-perature between 180 °C and 240 °C.
Description
PHN. 7737~
, ~ ' KTS/WJM/JEL~.
7-7-1975.
~Method of etching a pattern n glass".
The invention relates to a ~ethod of etching a pattern in glass and to products manufactured by this method.
United States Patent 3,489,6Z4 describes such a method in which first via a pyrolysable tin compound at an increased temperature a uniform layer of tin oxide and then a layer of an etch-resist material adapted to be modified by light are deposited on the glass surface~ the latter layer is exposed to light and then developed so that a coating according to the negative of a pattern desired in the glass is left, and finally the uncovered glass surface is exposed to the action of an etchant which contains h~drofluoric acid.
The tin oxide is deposited by heating the glass to a temperature between 400~ and the so~tening temperature of the glass and then spraying a liluid of dissolved pyrolysable tin compound on to the glass. This tin oxide, which is of a complex structure in which a chemical bond to the glass plays a part, ensures as an intermediate layer that the light-modifiable etch- resist layer adheres to the glass surface, for none of the usual photosensitive resists has sufficient adherence to glass.
Positive and negative photoresists are available, i.e.
resists which are soluble in a given reagent and become insoluble after exposure and resists which are insoluble
, ~ ' KTS/WJM/JEL~.
7-7-1975.
~Method of etching a pattern n glass".
The invention relates to a ~ethod of etching a pattern in glass and to products manufactured by this method.
United States Patent 3,489,6Z4 describes such a method in which first via a pyrolysable tin compound at an increased temperature a uniform layer of tin oxide and then a layer of an etch-resist material adapted to be modified by light are deposited on the glass surface~ the latter layer is exposed to light and then developed so that a coating according to the negative of a pattern desired in the glass is left, and finally the uncovered glass surface is exposed to the action of an etchant which contains h~drofluoric acid.
The tin oxide is deposited by heating the glass to a temperature between 400~ and the so~tening temperature of the glass and then spraying a liluid of dissolved pyrolysable tin compound on to the glass. This tin oxide, which is of a complex structure in which a chemical bond to the glass plays a part, ensures as an intermediate layer that the light-modifiable etch- resist layer adheres to the glass surface, for none of the usual photosensitive resists has sufficient adherence to glass.
Positive and negative photoresists are available, i.e.
resists which are soluble in a given reagent and become insoluble after exposure and resists which are insoluble
- 2 -- PHN. 7737-~ 7-7-1975.
in a reag-nt and become soluble in it after exposure respectively. Removing the soluble portions of the resist in the suitable solvent is referred to as developing.
After development the glass remains covered, via a tin oxide layer, with the exposed etch resist layer in the areas outside the pattern to be etched. The glass in the pattern parts is coated with a layer of tin oxide which first must ba removed. For this purpose the tin oxide is for so~e time maintained in contact with an acid solution under strongly reducing conditions, for example a HCl solution containing ~inc powder in contact with the tin oxide.
In practice the adherence of the etch-resist material to the tin oxide is found to be Fomparatively poor; hence the end result often leaves much to be desired.
The present invention provides a method the result of which is of appre~iably higher quality. In addition the method has further advantages over the above-described method.
The method of etching a pattern in glass by depositing first~ via a pyro~ysable metal compound at an increased temperature, a uniform metal of a metal oxide and then a layer of a light-modifiable etch-resist mate-rial on to the glass surface, e~posing the latter layer to light and then developing it so that an etchant-re-sistant coating according to the negative of a desired pattern in the glass i9 left, and subjecting the uncovered 3L5~
glass surface to the action of an etchant which contains hydro~luoric acid, according to the invention is character-ized in that the glass sur~ace is brought into contact with a pyrolysable titanium compound at a temperature between loO C and 240C.
The titanium dioxide, which in this manner is deposited at a far lower temperature than the tin oxide in the known method, has an amorphous structure and is an excellent adherence-intermediary for the etch-resist material. In view of de~ormation o~ the glass the lower temperature is ~ar more attractive.
The titanium dioxide is slowly dissolved in the etchant containing hydrofluoric acid. Because the layer of titanium dioxide need only be very thin ~at most 0.1 /um) and moreover is slightly porous, it can be removed comparatively rapidly. However, the di~erence in rate of the solution also results in that no under-etching takes place. In any case, in the method accord-ing to the invention, the additional processing step required in the method using tin oxide is dispensed with.
The pyrolysable titanium compound which can be used in the method according to the invention can be selected from organotitanium compound~ such as titanium acetylacetonate or isopropyltitanate. To obtain increased e ~ ng depths the glass pre~erably ~irst is subjected to a roughening treatment as described in Canadian Patent 1,000,131 PHN. 7737.
7-7-1975.
The uses of the etche~ product obtained by the method according to the invention may be of various natu-res, such as a stereotype for printing methods, a master for information recorded by optical means or an anode pl~te for a display panel.
The invention will now be illustrated by Examples.
Exam~
A sheet of soda-lime glass i5 ultrasonically cleaned for 5 minutes in a bath containing 1 l of ~l2S04 and 35 ml of a saturated R2Cr207 solution in H20, and subsequently rinsed for 1 minute in flowing de-ionized water. The sheet then is cleaned for 5 minutes in isopro----15 panol vapour. After cooling the plate is pulled up from a 5 ~ by weight solution of titanium acetylacetonate in isopropanol at a rate of 2.5 cm/min. The sheet is dried at 220C for 10 minutes and then by pulling up coat-ed with a photoresist which is commercially available under the trade name Shipley AZ 1350H. The photoresist is dried at 70C for 10 minutes and then exposed for 1 minute behind a negative by a high-pressure mercury vapour lamp (type HPR 125W) at a distance of 30 cm. The exposed photoresist is dissolved (developed) with Shipley . ,~........... ~ ~AZ developer (duration 2 m:inutes) 9 rinsed and dried. The glass sheet locally covered with photoresist is after-dried in an oven at 120C for 5 minutes~ The glass then .
~ rr~le~n~r~c is etched by immersing it in an aqueous HF solution. The etching depth is determined by the time of treatment and the concentration of the HF solution. The etching rates for various concentrations are 10 % HF 1-5 /um/min.
20 % HF 5 /um/min.
30 % HF 10 /um/min.
40 % HF 30 /um/min.
The method described enables patterns 20 /um deep to be etched. The underetching factor is 0.5. The etching depth has been measured with a Talysurf 10*.
If patterns of greater depth are to be etched, the photoresist must have better adherence to the glass.
Then a method as described in Canaclian Patent 1,000,131 is used. The soda-lime glass then first is mechanically roughened by a mechanical grinding operation using silicon carbide powder (SiC) having a grain coarseness of 44 (grain 240 according to FEPA standard) and then for 10 seconds chemically treated with 10 % HF solution, rinsed and dried. Subsequently an amorphous TiO2 layer and a photoresist are deposited in the manner described in Example I. After this treatment patterns at least 200 /um deep can be etched. The underetching factor remains 0.5.
Example III.
A sheet o~ a borosilicate glass is cleaned * TrNdemark 6 -PHN. 7737.
9 7-7-1975.
and provided with an amorphous layer of TiO2 and a photo-resist coating in the manner described in Example I.
When etching with 40 % HF the depth as a function of time is 1 minute 12 /um.
2 minutes 17 /um.
in a reag-nt and become soluble in it after exposure respectively. Removing the soluble portions of the resist in the suitable solvent is referred to as developing.
After development the glass remains covered, via a tin oxide layer, with the exposed etch resist layer in the areas outside the pattern to be etched. The glass in the pattern parts is coated with a layer of tin oxide which first must ba removed. For this purpose the tin oxide is for so~e time maintained in contact with an acid solution under strongly reducing conditions, for example a HCl solution containing ~inc powder in contact with the tin oxide.
In practice the adherence of the etch-resist material to the tin oxide is found to be Fomparatively poor; hence the end result often leaves much to be desired.
The present invention provides a method the result of which is of appre~iably higher quality. In addition the method has further advantages over the above-described method.
The method of etching a pattern in glass by depositing first~ via a pyro~ysable metal compound at an increased temperature, a uniform metal of a metal oxide and then a layer of a light-modifiable etch-resist mate-rial on to the glass surface, e~posing the latter layer to light and then developing it so that an etchant-re-sistant coating according to the negative of a desired pattern in the glass i9 left, and subjecting the uncovered 3L5~
glass surface to the action of an etchant which contains hydro~luoric acid, according to the invention is character-ized in that the glass sur~ace is brought into contact with a pyrolysable titanium compound at a temperature between loO C and 240C.
The titanium dioxide, which in this manner is deposited at a far lower temperature than the tin oxide in the known method, has an amorphous structure and is an excellent adherence-intermediary for the etch-resist material. In view of de~ormation o~ the glass the lower temperature is ~ar more attractive.
The titanium dioxide is slowly dissolved in the etchant containing hydrofluoric acid. Because the layer of titanium dioxide need only be very thin ~at most 0.1 /um) and moreover is slightly porous, it can be removed comparatively rapidly. However, the di~erence in rate of the solution also results in that no under-etching takes place. In any case, in the method accord-ing to the invention, the additional processing step required in the method using tin oxide is dispensed with.
The pyrolysable titanium compound which can be used in the method according to the invention can be selected from organotitanium compound~ such as titanium acetylacetonate or isopropyltitanate. To obtain increased e ~ ng depths the glass pre~erably ~irst is subjected to a roughening treatment as described in Canadian Patent 1,000,131 PHN. 7737.
7-7-1975.
The uses of the etche~ product obtained by the method according to the invention may be of various natu-res, such as a stereotype for printing methods, a master for information recorded by optical means or an anode pl~te for a display panel.
The invention will now be illustrated by Examples.
Exam~
A sheet of soda-lime glass i5 ultrasonically cleaned for 5 minutes in a bath containing 1 l of ~l2S04 and 35 ml of a saturated R2Cr207 solution in H20, and subsequently rinsed for 1 minute in flowing de-ionized water. The sheet then is cleaned for 5 minutes in isopro----15 panol vapour. After cooling the plate is pulled up from a 5 ~ by weight solution of titanium acetylacetonate in isopropanol at a rate of 2.5 cm/min. The sheet is dried at 220C for 10 minutes and then by pulling up coat-ed with a photoresist which is commercially available under the trade name Shipley AZ 1350H. The photoresist is dried at 70C for 10 minutes and then exposed for 1 minute behind a negative by a high-pressure mercury vapour lamp (type HPR 125W) at a distance of 30 cm. The exposed photoresist is dissolved (developed) with Shipley . ,~........... ~ ~AZ developer (duration 2 m:inutes) 9 rinsed and dried. The glass sheet locally covered with photoresist is after-dried in an oven at 120C for 5 minutes~ The glass then .
~ rr~le~n~r~c is etched by immersing it in an aqueous HF solution. The etching depth is determined by the time of treatment and the concentration of the HF solution. The etching rates for various concentrations are 10 % HF 1-5 /um/min.
20 % HF 5 /um/min.
30 % HF 10 /um/min.
40 % HF 30 /um/min.
The method described enables patterns 20 /um deep to be etched. The underetching factor is 0.5. The etching depth has been measured with a Talysurf 10*.
If patterns of greater depth are to be etched, the photoresist must have better adherence to the glass.
Then a method as described in Canaclian Patent 1,000,131 is used. The soda-lime glass then first is mechanically roughened by a mechanical grinding operation using silicon carbide powder (SiC) having a grain coarseness of 44 (grain 240 according to FEPA standard) and then for 10 seconds chemically treated with 10 % HF solution, rinsed and dried. Subsequently an amorphous TiO2 layer and a photoresist are deposited in the manner described in Example I. After this treatment patterns at least 200 /um deep can be etched. The underetching factor remains 0.5.
Example III.
A sheet o~ a borosilicate glass is cleaned * TrNdemark 6 -PHN. 7737.
9 7-7-1975.
and provided with an amorphous layer of TiO2 and a photo-resist coating in the manner described in Example I.
When etching with 40 % HF the depth as a function of time is 1 minute 12 /um.
2 minutes 17 /um.
3 minutes 21 /um.
Using a pretreatment as described in Example I the maximum etching depth is 8 /um whereas using a pretreatment as described in Example II the etching depth is indefinite.
The underetching factor is 0.5, Example IV.
A quartz sheet is pretreated in the manner des-cribed in Example I. When etching in 40 % HF the following depths are obtained as functions of etching time 1 minute 4 /um.
2 minutes 6 /um.
3 minutes 8 /um.
With a pretreatment as described in Example I the maximum etching depth is 3 /um whereas with a pretreatment as described in Example II the etching depth is indefinite.
The underetching factor is 0.5.
Using a pretreatment as described in Example I the maximum etching depth is 8 /um whereas using a pretreatment as described in Example II the etching depth is indefinite.
The underetching factor is 0.5, Example IV.
A quartz sheet is pretreated in the manner des-cribed in Example I. When etching in 40 % HF the following depths are obtained as functions of etching time 1 minute 4 /um.
2 minutes 6 /um.
3 minutes 8 /um.
With a pretreatment as described in Example I the maximum etching depth is 3 /um whereas with a pretreatment as described in Example II the etching depth is indefinite.
The underetching factor is 0.5.
Claims (4)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Method of etching a pattern in glass by first depositing on the glass surface via a pyrolysable metal compound at an increased temperature a uniform layer of a metal oxide and then a layer of an etching resist material adapted to be modified by light, by exposing and then developing the latter layer so that an etchant-resistant covering according to the negative of a pattern desired in the glass is left, and by subjecting the uncovered glass surface to the action of an etchant which contains hydro-fluoric acid, characterized in that the glass surface is brought into contact with a pyrolysable titanium compound at a temperature between 180°C
and 240°C.
and 240°C.
2. Method as claimed in claim 1, characterized in that the thickness of the obtained titanium dioxide layer is at most 0.1 µm.
3. A method according to claim 1 characterized in that the glass is roughened prior to the application of the pyrolysable titanium compound.
4. A method according to claim 1, 2 or 3 wherein the pyrolysable titanium compound is selected from the group titanium acetylacetonate or isopropyltitanate,
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL7412384A NL7412384A (en) | 1974-09-19 | 1974-09-19 | METHOD OF ETCHING A PATTERN IN GLASS. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1061159A true CA1061159A (en) | 1979-08-28 |
Family
ID=19822131
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA235,541A Expired CA1061159A (en) | 1974-09-19 | 1975-09-16 | Method of etching a pattern in glass |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS5156820A (en) |
| CA (1) | CA1061159A (en) |
| DE (1) | DE2541205A1 (en) |
| FR (1) | FR2285639A1 (en) |
| GB (1) | GB1506961A (en) |
| NL (1) | NL7412384A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3343704A1 (en) * | 1983-12-02 | 1985-06-13 | Siemens AG, 1000 Berlin und 8000 München | METHOD AND DEVICE FOR SETTING HOLE GRID PLATES, ESPECIALLY FOR PLASMA CATHODE DISPLAY |
| DE19820754C2 (en) * | 1998-05-08 | 2001-08-30 | Guenter Seidl | Method for creating a structure on a substrate |
| KR102583733B1 (en) * | 2023-03-03 | 2023-09-27 | 백도 | Waterproofing device using Micro-cement of Crack repair material and Method for reinforcing concrete |
-
1974
- 1974-09-19 NL NL7412384A patent/NL7412384A/en not_active Application Discontinuation
-
1975
- 1975-09-16 DE DE19752541205 patent/DE2541205A1/en not_active Withdrawn
- 1975-09-16 JP JP11103475A patent/JPS5156820A/en active Pending
- 1975-09-16 GB GB3800775A patent/GB1506961A/en not_active Expired
- 1975-09-16 CA CA235,541A patent/CA1061159A/en not_active Expired
- 1975-09-18 FR FR7528637A patent/FR2285639A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5156820A (en) | 1976-05-18 |
| NL7412384A (en) | 1976-03-23 |
| FR2285639B1 (en) | 1978-05-19 |
| DE2541205A1 (en) | 1976-04-08 |
| FR2285639A1 (en) | 1976-04-16 |
| GB1506961A (en) | 1978-04-12 |
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