# Patent

## Title
Transparent LAS glass ceramics produced with alternative environmentally acceptable fining agents

## Abstract

The transparent glass ceramic with low thermal expansion is produced from a glass that is fined with a combination of environmentally friendly fining agents, specifically a combination of SnO2 with at least one of Sb2O3, SO42−, Br− and Cl−. The glass is free of arsenic and is preferably made from a mixture of SiO2, Al2O3, Li2O, TiO2, ZrO2 and ZnO. A mirror support for astronomy and a prism for LCD lithography are advantageously made from this glass ceramic.

## Background
CROSS-REFERENCE
The invention described and claimed herein below is also described in German Patent Application DE 10 2010 002 188.1, filed on Feb. 22, 2010 in Germany. The aforesaid German Patent Application, whose subject matter is incorporated herein by explicit reference thereto, provides the basis for a claim of priority of invention for the invention claimed herein below under 35 U.S.C. 119 (a)-(d).
BACKGROUND OF THE INVENTION
1. The Field of the Invention
The present invention relates to transparent glass ceramics having low thermal expansion, also called “zero expansion”, containing only environmentally acceptable fining agents, or being fined only with environmentally acceptable fining agents, respectively, as well as to the uses of the glass ceramics according to the present invention.
2. The Related Art
Among glass ceramics having low thermal expansion, lithium-aluminium-silicon oxide glass ceramics, which are also known in the art as LAS glass ceramics, are so-called “zero expansion materials”. A well-known type of this sort of glass ceramic material, known as ZERODUR®, is commercially available in three different thermal expansion classes of 0 to 2 and has different coefficients of linear thermal expansion a in a temperature range of 0° to 50° C. as shown in Table I herein below.







TABLE I







Linear Thermal Expansion Coefficients of Different Classes











Coefficients of linear



Expansion class
thermal expansion α







0
0 ± 0.02 · 10−6/K



1
0 ± 0.05 · 10−6/K



2
0 ± 0.10 · 10−6/K










With respect to melting of glass the term “fining” means the removal of gas bubbles from the melt. To achieve the highest quality in terms of removal of foreign gas and bubbles a thorough mixing and degasifying of the molten mixture is necessary. The behavior of gases and bubbles, respectively, in the glass melt as well as their removal are described for example in “Glastechnische Fabrikationsfehler”, edited by H. Jebsen-Marwedel and R. Brückner, third edition, 1980, Springer Verlag, on pages 195 ff.
Chemical fining methods are most often used. Their principle of operation is that compounds which undergo decomposition and release gases, compounds which are volatile at elevated temperatures or compounds which release gases in an equilibrium reaction at higher temperatures are added to the melt.
Sodium sulfate, for example, which is used for fining soda-lime glass, belongs to a first group of these compounds used for chemical fining. In this case, the release of SO2 and O2 takes place in a temperature range of 1300° C. to 1450° C. with a maximum at 1380° C. This temperature range approximately corresponds to the fining range of such glasses.
Compounds, which are volatile at high temperatures due to their vapor pressure and thus act as a gas, such as halides, sodium chloride or different fluorides, belong to a second group. Thus for example a series of boron silicate glasses are fined with sodium chloride. The fining agents of this second group are designated “volatilization fining agents”.
A last group of fining agents comprises the so-called redox fining agents, such as arsenic oxide and antimony oxide. In practice, they are used most often. In the respective fining methods covalent ions, which can be present in at least two inter-related oxidation states in a temperature-dependent equilibrium with each other so that a gas, usually oxygen, is released at high temperatures, are used as redox fining agents.
For arsenic oxide as an example, the redox equilibrium that occurs in the melt can be represented by the following equation (I):

As2O5As2O3+O2↑  (I),

The equilibrium constant K for equation (I) is given by equation (II):




  
    
      
        
          K
          ⁡
          
            (
            T
            )
          
        
        =
        
          
            
              
                aAs
                2
              
              ⁢
              
                
                  O
                  3
                
                ·
                
                  z
                  ⁡
                  
                    (
                    
                      O
                      2
                    
                    )
                  
                
              
            
            
              
                aAs
                2
              
              ⁢
              
                O
                5
              
            
          
          .
        
      
    
    
      
        (
        II
        )
      
    
  




In this equation aAs2O3 and aAs2O5 represent the respective activities of the arsenic trioxide and arsenic pentoxide and z (O2) represent the fugacity (of the oxygen). The equilibrium constant K strongly depends on the temperature and a defined oxygen fugacity z (O2) can be adjusted with the temperature and the activity of the oxidic arsenic compounds.
A disadvantage of many redox fining agents is that they are harmful to the environment; at least they are not environmentally acceptable. Particularly this applies to arsenic oxide. However this particular fining agent has a property which is useful: The release of the fining gas O2 has two maxima at about 1250° C. and at about 1600° C. These maxima correspond to the temperature range of melting, on the one hand, and the temperature range of fining, on the other hand. This sort of fining behavior is desirable, but arsenic trioxide is strongly toxic and undoubtedly classified as carcinogenic. Anionic arsenic is already present as arsenite and arsenate in high concentrations in the ground water of many countries. This is the reason that As2O3 is to be forbidden in several countries in the next years.
DE 1 596 860 discloses a method for the production of transparent glass ceramics having low thermal expansion. As a fining agent 0.3 to 0.5% by weight of As2O3 is used. Environmentally acceptable fining agents are not discussed.
U.S. Pat. No. 4,851,372 describes transparent glass ceramics which are fined with 0 to 1.5% by weight of As2O3 or Sb2O3. Also in this case, there is no discussion about environmentally acceptable fining agents.
EP 1 864 952 A1 describes aluminium silicate and lithium aluminium silicate glass ceramics containing amounts of SnO2 and/or CeO2 of 0.01 to 5.0 percent by mass each, based on the oxides. However, the cerium oxide affects the transmissions of the glass ceramics.
US 2007/0281849 A1 describes glass ceramics containing amounts of SnO2 and/or CeO2 of 0.01 to 5.0 percent by mass, based on the oxides. The presence of cerium oxide is a disadvantage, because it may result in an undesired coloration.
DE 199 39 771 A1 describes a fining method for glass melts during which a fining gas is produced in the glass melt by a fining agent. As fining agents redox compounds, in particular redox oxides such as SnO2, CeO2, Fe2O3, ZnO, TiO2, V2O5, MoO3, WO3, Bi2O5, PrO2, Sm2O3, Sb2O5, Eu2O3, TbO2 and/or Yb2O3, can be used. In addition, metal oxides, such as ZnO, As2O3, Sb2O3, Bi2O3 and/or SnO, are added, which release oxygen and change into the metallic state, during the fining operation. Many of these fining agents and their combinations, such as CeO2 and Fe2O3, change the transmission properties of the glass ceramic in a disadvantageous manner.
SUMMARY OF THE INVENTION
It is the object of the present invention to provide transparent glass ceramics having low thermal expansion which contain alternative environmentally acceptable fining agents and preferably avoid the disadvantages of the above-described environmentally unacceptable fining agents.
The object of the present invention is attained by the subject matter of the patent claims appended herein below.
The object is in particularly attained by a transparent glass ceramic having a low thermal expansion, comprising the following composition, % by weight, based on oxide content:
















SiO2
35 to 70



Al2O3
17 to 35



Li2O
2 to 6



TiO2
0 to 6



ZrO2
0 to 6



TiO2 + ZrO2
0.5 to 9



ZnO
0.5 to 5,










wherein the glass ceramic is produced by fining with SnO2 and at least one further fining agent.



The method of producing these glass ceramics comprises adding to a crystallizable glass a mixture of fining agents that permits production of a glass ceramic having low thermal expansion without using arsenic oxide. Preferred mixtures of fining agents are mixtures of SnO2 with the further fining agents Sb2O3, SO42−, Br− and/or Cl−. In order to obtain glass ceramics with good transparencies, the fining agents should be used in the correct proportions, i.e. in a preferred molar ratio of SnO2 to further fining agents of 1:2 to 2:1.
The respective fining method of the invention is a so-called mixed fining. In production the fining using SnO2 as a fining agent results in a chemical equilibrium represented by the following equation (III):

2SnO22SnO+O2  (III),

Thus the glass ceramic according to the present invention comprises SnO, which has been formed from SnO2, and at least one further component, which has been formed from a fining agent preferably selected from the group consisting of Sb2O3, SO42−, Br− and Cl−.
Preferably the respective components, which result from the fining agents SnO2 and Sb2O3 or SO42− or Br− or Cl−, are contained in the glass ceramic according to the present invention. When SO42−, Br− or Cl− act as fining agents, they are added to the starting melt in the form of their alkali or alkaline earth salts.
According to the present invention combinations of fining agents are provided which can provide similar fining conditions as As2O3 which has already been described above as an environmentally unacceptable fining agent due to its toxic and carcinogenic properties. In this case, the fining agents satisfy the further condition that no significant changes in a proven and tested melting process are necessary. A nearly similar fining effect can be achieved in comparison to the fining agent arsenic trioxide without the need for a change in process parameters. This significantly reduces costs and thus allows an economically advantageous production of the ceramics according to the present invention.
Sb2O3 as a fining agent has a high O2 release peak at about 1150° C. which overlaps the O2 release peak of As2O3 at 1250° C. The sulfate releases SO2 and O2 at about 1300° C. Thus, the combination of both fining agents is suitable for replacing the toxic As2O3. Br− and Cl− are released as HX (X=Cl, Br) already at lower temperatures. This results in the release of less fining gas than Sb2O3 or sulfate at higher temperatures (>1200° C.) in the case of these latter fining agents. Therefore these latter fining agents are used in a supportive manner.
In the selection of suitable combinations of fining agents the fact that none of the fining agents used should cause coloration of the glass ceramic product must be considered. Therefore these glass ceramics are preferably not fined with CeO2 so that the glass ceramics are essentially free of CeO2.
According to the present invention the glass ceramic contains at least one component, which has been formed from a fining agent, in an amount of 0.001 to 2% by mol each, based on the total amount of glass ceramic present.
When it is said that the glass ceramics are “free of”, “do not contain”, or are “essentially free of” a certain component or a certain component is not used in the preparation of the glass ceramic, this means that the respective component can only be present as an impurity in very small amounts. These very small amounts are typically below 100 ppm, preferably below 50 ppm.
Preferably the present glass ceramics are free of iron oxides because iron can affect the transmissions of the glass ceramics of the present invention. The glass ceramics are also preferably free of vanadium oxides.
The glass ceramic according to the present invention preferably contains a component resulting from a fining agent in an amount of 0.001 to 2% by mol.
The glass ceramic according to the present invention preferably contains a component resulting from the fining agent SnO2, in particular SnO, in a proportion of 0.001 to 2% by mol.
In the present invention the term “zero expansion materials” means glass ceramics with a coefficient of linear thermal expansion that is zero or near zero in a defined temperature range.
The glass ceramics according to the present invention have a thermal expansion of expansion class 2, preferably of expansion class 1, and more preferably of expansion class 0. A special material, ZERODUR®K20, which for example is produced from ZERODUR® by a further step of additional ceramization has a coefficient of linear thermal expansion, or expansion of length, of 1.5 ppm/K.
The glass ceramic according to the present invention preferably comprises one or more of the following further components, in % by weight, based on oxide content:
















B2O3
0 to 6



Na2O
0 to 2



K2O
0 to 2



MgO
0 to 5



P2O3
0 to 17



CaO
0 to 4



BaO
0 to 5



SrO
0 to 5.










Preferably the glass ceramic according to the present invention does not contain As2O3, CeO2 and/or PbO. As2O3 and PbO are toxic and are a heavy burden for the environment. CeO2 results in a very strong self-coloring of the glass ceramic which is not desirable for the glass ceramics according to the present invention. This change in color may possibly be further intensified by formation of a colored complex of TiO2—CeO2.
A further reason not to use of CeO2 is that in the production process of the glass ceramic oxygen is released already between 950° C. and 1050° C. CeO2 has a release peak at about 1000° C. which is too low for replacing As (first release peak at 1250° C.). But the fining temperature should be 1250° C. so that it is in accordance with the temperature of the first release peak of As2O3 for a good fining effect. It would be very expensive and disadvantageous for the high homogeneity and reproducibility provided so far to change the melting process so that it can be adjusted to the earlier release of oxygen in the fining process using CeO2. Only in this way a fining effect can be obtained which is as good as the one which is achieved by the use of the fining agent As2O3. However this possibility does not result in an economic alternative.
Glass ceramics comprising one or more crystal phases selected from the group consisting of high quartz, mixed high quartz crystal, keatite, mixed keatite crystal and β-eucryptite are preferable in the glass ceramics according to the present invention.
Preferably the glass ceramics according to the present invention only contain small amounts of the residual gases CO2, SO2, O2, argon or N2 or combinations thereof. The content of the residual gas, for example in ZERODUR®, which has been produced by the use of toxic As2O3 or by the use of fining combinations according to the present invention, such as SnO2/SO2 or SnO2/Sb2O3, is listed in table II. From the values in table II it becomes clear that the content of residual gas in the glass ceramic with the fining combinations according to the present invention is the same or even significantly lower than the respective content resulting from the use of the fining agent As2O3.







TABLE II







Content of Residual Gas in Zerodur ® for Different Fining Agents
















Ar/ppm
N2/ppm






quali-
quali-


Glass
CO2/ppm
SO2/ppm
O2/ppm
tative
tative















Production-
9.3 ± 0.9
0.8 ± 0.2
204 ± 19
<0.1
1.7


ZERODUR ®-


As2O3


Laboratory-
10.2 ± 1.5 
<0.5
228 ± 39
0.3
1


ZERODUR ®-


As2O3


Laboratory-
4.5 ± 1.5
1.2 ± 0.2
225 ± 20
<0.1
0.6


ZERODUR ®-


SnO2/SO2


Laboratory-
7.6 ± 0.9
<0.5
204 ± 20
0.3
0.3


ZERODUR ®-


SnO2/Sb2O3









Preferably the glass ceramic according to the present invention is used in lithography, astronomy or as a precision element. In lithography the glass ceramic is preferably used in LCD lithography and in microlithography. Further preferably, the glass ceramic according to the present invention is used in EUV lithography.
The use of a combination of SnO2 together with a further fining agent for fining of glasses, which are suitable for the production of glass ceramics, is also an aspect of this invention. These glass ceramics are those described herein. A method of producing a glass ceramic according to this invention with the process steps described in this description is also an aspect of this invention.
Mirror supports used in astronomy preferably comprise a glass ceramic according to the present invention. In addition mirror supports for LCD lithography and EUV lithography also preferably comprise a glass ceramic according to the present invention. Preferably, the mirror support is a light-weight mirror support. Prisms used in LCD lithography preferably comprise a glass ceramic according to the present invention. These mirror supports and prisms are also an important aspect of the present invention.
While the invention has been illustrated and described as embodied in transparent LAS glass ceramics produced with alternative environmentally acceptable fining agents and uses thereof, it is not intended to be limited to the details shown, since various modifications and changes may be made without departing in any way from the spirit of the present invention.
Without further analysis, the foregoing will so fully reveal the gist of the present invention that others can, by applying current knowledge, readily adapt it for various applications without omitting features that, from the standpoint of prior art, fairly constitute essential characteristics of the generic or specific aspects of this invention. What is claimed is new and is set forth in the following appended claims.

## Claims

1. A transparent glass ceramic having low thermal expansion and a composition, in % by weight, based on oxide content, of:
















SiO2
 35 to 70



Al2O3
 17 to 35



Li2O
  2 to 6



TiO2
  0 to 6



ZrO2
  0 to 6



TiO2 + ZrO2
0.5 to 9



ZnO
0.5 to 5,









wherein the glass ceramic is produced by fining with SnO2 and at least one further fining agent selected from the group consisting of Sb2O3, SO42−, Br− and Cl−;
wherein a molar ratio of the SnO2 to the at least one further fining agent is from 1:2 to 2:1,
wherein the transparent glass ceramic has a thermal expansion coefficient in a range of −0.10·10−6/K to +0.10·10−6/K in a temperature range of 0° C. to 50° C., and
wherein the glass ceramic contains one or more crystal phases selected from the group consisting of high quartz, mixed high quartz crystal, keatite, mixed keatite crystal and β-eucryptite.

2. The glass ceramic according to claim 1, further comprising at least one additional component formed from a fining ingredient selected from the group consisting of Sb2O3, SO42− and Cl−.

3. The glass ceramic according to claim 2, wherein said at least one additional component formed from the fining ingredient is contained in an amount of 0.001 to 2% by mol each, based on a total amount of the glass ceramic.

4. The glass ceramic according to claim 1, further comprising a component formed from said SnO2 in an amount of 0.001 to 2% by mol.

5. The glass ceramic according to claim 1, wherein said thermal expansion coefficient is from −0.05·10−6/K. to +0.05·10−6/K in said temperature range of 0° C. to 50° C.

6. The glass ceramic according to claim 1, additionally comprising one or more of the following components, in % by weight, based on oxide content:
















B2O3
0 to 6



Na2O
0 to 2



K2O
0 to 2



MgO
0 to 5



P2O3
0 to 17



CaO
0 to 4



BaO
0 to 5



SrO
0 to 5.

7. The glass ceramic according to claim 1, which is free of As2O3, CeO2 and/or PbO.

8. An element for lithography, in particular for LCD lithography and microlithography, in astronomy or as a precision element, said element comprising a glass ceramic according to claim 1.

9. A method of fining glass to be used for producing a transparent glass ceramic, wherein said transparent glass ceramic has a low thermal expansion and a composition, in % by weight, based on oxide content of:
















SiO2
 35 to 70



Al2O3
 17 to 35



Li2O
  2 to 6



TiO2
  0 to 6



ZrO2
  0 to 6



TiO2 + ZrO2
0.5 to 9



ZnO
0.5 to 5,









wherein the glass ceramic is produced by fining with SnO2 and at least one further fining agent selected from the group consisting of Sb2O3, SO42− and Cl−;
wherein a molar ratio of the SnO2 to the at least one further fining agent is from 1:2 to 2:1,
wherein the transparent glass ceramic has a thermal expansion coefficient in a range of −0.10·10−6/K to +0.10·10−6/K in a temperature range of 0° C. to 50° C., and

wherein the glass ceramic contains one or more crystal phases selected from the group consisting of high quartz, mixed high quartz crystal, keatite, mixed keatite crystal and β-eucryptite, and wherein said method comprises fining with SnO2 and at least one further fining agent selected from the group consisting of Sb2O3, SO42− and Cl− in a molar ratio of 1:2 to 2:1.

10. A mirror support for astronomy, said mirror support comprising a glass ceramic according to claim 1.

11. The mirror support according to claim 10, which is light-weight.

12. A prism for LCD lithography, said prism comprising a glass ceramic according to claim 1.

13. A mirror support for LCD lithography, said mirror support comprising a glass ceramic according to claim 1.

14. A method of producing a glass ceramic according to claim 1, said method comprising the step of fining a glass melt with a combination of fining agents comprising SnO2 and at least one further fining agent selected from the group consisting of Sb2O3, SO42−, Br− and Cl−.

15. The glass ceramic according to claim 1, which is free of vanadium oxides.

16. The glass ceramic according to claim 1, containing less residual gas than a glass ceramic of the same composition, except that the SnO2 and the at least one further refining agent are replaced by As2O3.