DETAILED ACTION
Notice of Pre-AIA or AIA Status
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Claim Rejections - 35 USC § 102
In the event the determination of the status of the application as subject to AIA 35 U.S.C. 102 and 103 (or as subject to pre-AIA 35 U.S.C. 102 and 103) is incorrect, any correction of the statutory basis (i.e., changing from AIA to pre-AIA ) for the rejection will not be considered a new ground of rejection if the prior art relied upon, and the rationale supporting the rejection, would be the same under either status.
The following is a quotation of the appropriate paragraphs of 35 U.S.C. 102 that form the basis for the rejections under this section made in this Office action:
A person shall be entitled to a patent unless –
(a)(1) the claimed invention was patented, described in a printed publication, or in public use, on sale, or otherwise available to the public before the effective filing date of the claimed invention.
Claims 1-10 and 15 are rejected under 35 U.S.C. 102(a)(1) as being anticipated by Danto et al. (EP 1642870) [citations from machine translation appended to this action]
Regarding claim 1, Danto discloses a phase change material comprising, in at%, from 1% to 40% of Ge, from 40% to 90% of Te, and from 0% to less than 5% of Sb, and
further comprising from 1% to 59% of one or more selected from Si, AI, Ga, Sn,
Bi, Cu, Ag, Zn, Y, In, Ca, and Mg, and from 1% to 59% of Ga + Ag (paragraphs 0015-0021).
Regarding claim 2, Danto further discloses wherein Te/Ge, a content ratio of Te to Ge, is from 2 to 8 (paragraphs 0015-0021).
Regarding claim 3, Danto further discloses comprising from 0% to less than 5% of Sb + As (paragraphs 0015-0021).
Regarding claim 4, Danto further discloses wherein a crystallization temperature Tx is 150°C or higher (paragraph 0015 and table 1 and paragraph 0026).
Regarding claim 5, Danto further discloses wherein a crystalline melting point Tm is 600°C or lower (table 1 and paragraph 0026).
Regarding claim 6, Danto further discloses wherein (Tm - Tx), a difference between the crystalline melting point Tm and the crystallization temperature Tx, is 400°C or lower (table 1 and paragraph 0026).
Regarding claim 7, Danto discloses a phase change material comprising, in at%, from 1% to 40% of Ge, from 40% to 90% of Te, from 41% to 99% of Ge + Te, and from 0% to less than 5% of Sb, and from 1% to 59% of Ga + Ag (paragraphs 0015-0021),
wherein (Tm - Tx), a difference between a crystalline melting point Tm and a
crystallization temperature Tx, is 400°C or lower (table 1 and paragraph 0026).
Regarding claim 8, Danto discloses a phase change material comprising, in at%, from 1% to 40% of Ge, from 40% to 90% of Te, from 41% to 99% of Ge + Te, and from 0% to less than 5% of Sb, and from 1% to 59% of Ga + Ag (paragraphs 0015-0021),
wherein when in a crystalline state, the phase change material comprises at least
one type of crystal selected from GeTe4, GeTe, Te, and Ga2Te3 (inherent given the chemical makeup of examples disclosed, Table 1 and paragraphs 0015-0026).
Regarding claim 9, Danto further discloses a target comprising the phase change material according to claim 1(Table 1 and paragraphs 0015-0026).
Regarding claim 10, Danto further discloses a thin film comprising the phase change material according to claim 1 (Table 1 and paragraphs 0015-0026).
Regarding claim 15, Danto further discloses comprising 1% to 59% of Ga (paragraphs 0015-0021).
Claim Rejections - 35 USC § 103
In the event the determination of the status of the application as subject to AIA 35 U.S.C. 102 and 103 (or as subject to pre-AIA 35 U.S.C. 102 and 103) is incorrect, any correction of the statutory basis (i.e., changing from AIA to pre-AIA ) for the rejection will not be considered a new ground of rejection if the prior art relied upon, and the rationale supporting the rejection, would be the same under either status.
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
Claims 1-14 are rejected under 35 U.S.C. 103 as being unpatentable over Sutou et al. (US 2012/0235110).
Regarding claim 1, Sutou discloses a phase change material comprising, in at%, from 1% to 40% of Ge, from 40% to 90% of Te, and from 0% to less than 5% of Sb, and
further comprising from 1% to 59% of one or more selected from Si, AI, Ga, Sn,
Bi, Cu, Ag, Zn, Y, In, Ca, and Mg (paragraphs 0012, 0027-0037). Sutou does not explicitly disclose from 1% to 59% of Ga +Ag. However, it would have been obvious to one of ordinary skill in the art at the time of filing to incorporate 1% to 59% of Ga +Ag into Sutou’s material given normal experimentation of Sutou’s teachings since Sutou discloses Al and Cu from 1% to 59% (paragraphs 0012, 0027-0037) and Al and Ga are both trivalent elements in Group IIIA of the periodic table sharing a lot in common, as such, would be deemed obvious substitutions under normal experimentation. Likewise with Cu and Ag, both being transition metals of Group 11 of the periodic table and both are known to be highly mobile in many chalcogenide materials and can participate in ionic/metallic switching mechanisms.
Regarding claim 2, Sutou further discloses wherein Te/Ge, a content ratio of Te to Ge, is from 2 to 8 (multiple examples such as ex 10-18, 23-26 given, figs. 1A-B and paragraphs 0012, 0027-0037).
Regarding claim 3, Sutou further discloses comprising from 0% to less than 5% of Sb + As (paragraphs 0012, 0027-0037).
Regarding claim 4, Sutou further discloses wherein a crystallization temperature Tx is 150°C or higher (multiple examples such as ex 10-18, 23-26 given, figs. 1A-B).
Regarding claim 5, Sutou further discloses wherein a crystalline melting point Tm is 600°C or lower (multiple examples such as ex 10-18, 27-29 given, figs. 1A-B).
Regarding claim 6, Sutou further discloses wherein (Tm - Tx), a difference between the crystalline melting point Tm and the crystallization temperature Tx, is 400°C or lower (multiple examples such as ex 10-18, 23 given, figs. 1A-B).
Regarding claim 7, Sutou discloses a phase change material comprising, in at%, from 1% to 40% of Ge, from 40% to 90% of Te, from 41% to 99% of Ge + Te, and from 0% to less than 5% of Sb (paragraphs 0012, 0027-0037),
wherein (Tm - Tx), a difference between a crystalline melting point Tm and a
crystallization temperature Tx, is 400°C or lower (multiple examples such as ex 10-18, 23 given, figs. 1A-B). Sutou does not explicitly disclose from 1% to 59% of Ga +Ag. However, it would have been obvious to one of ordinary skill in the art at the time of filing to incorporate 1% to 59% of Ga +Ag into Sutou’s material given normal experimentation of Sutou’s teachings since Sutou discloses Al and Cu from 1% to 59% (paragraphs 0012, 0027-0037) and Al and Ga are both trivalent elements in Group IIIA of the periodic table sharing a lot in common, as such, would be deemed obvious substitutions under normal experimentation. Likewise with Cu and Ag, both being transition metals of Group 11 of the periodic table and both are known to be highly mobile in many chalcogenide materials and can participate in ionic/metallic switching mechanisms.
Regarding claim 8, Sutou discloses a phase change material comprising, in at%, from 1% to 40% of Ge, from 40% to 90% of Te, from 41% to 99% of Ge + Te, from 0% to less than 5% of Sb, and from 0% to 59% of Ga (paragraphs 0012, 0027-0037),
wherein when in a crystalline state, the phase change material comprises at least
one type of crystal selected from GeTe4, GeTe, Te, and Ga2Te3 (inherent given the chemical makeup of examples such as ex 10-18, 23 given, figs. 1A-B). Sutou does not explicitly disclose from 1% to 59% of Ga +Ag. However, it would have been obvious to one of ordinary skill in the art at the time of filing to incorporate 1% to 59% of Ga +Ag into Sutou’s material given normal experimentation of Sutou’s teachings since Sutou discloses Al and Cu from 1% to 59% (paragraphs 0012, 0027-0037) and Al and Ga are both trivalent elements in Group IIIA of the periodic table sharing a lot in common, as such, would be deemed obvious substitutions under normal experimentation. Likewise with Cu and Ag, both being transition metals of Group 11 of the periodic table and both are known to be highly mobile in many chalcogenide materials and can participate in ionic/metallic switching mechanisms.
Regarding claim 9, Sutou further discloses a target comprising the phase change material according to claim 1(4, figs. 10A-B and paragraph 0092).
Regarding claim 10, Sutou further discloses a thin film comprising the phase change material according to claim 1 (4, figs. 10A-B and paragraph 0092).
Regarding claim 11, Sutou further discloses a memory element comprising the phase change material according to claim 1 (4, figs. 10A-B and paragraph 0092).
Regarding claim 12, Sutou further discloses a memory device comprising the memory element according to claim 11 (paragraph 92).
Regarding claim 13, Sutou discloses a method of recording information, the method comprising a step of recording information by applying a voltage to a memory layer comprising a phase change material and changing a phase of the memory layer from a first state to a second state (paragraphs 0092-0094),
wherein the memory layer comprises a phase change material comprising, in
at%, from 1% to 40% of Ge, from 40% to 90% of Te, and from 0% to less than 5% of
Sb, and further comprises from 1% to 59% of one or more selected from Si, Al, Ga, Sn,
Bi, Cu, Ag, Zn, Y, In, Ca, and Mg (paragraphs 0012, 0027-0037). Sutou does not explicitly disclose from 1% to 59% of Ga +Ag. However, it would have been obvious to one of ordinary skill in the art at the time of filing to incorporate 1% to 59% of Ga +Ag into Sutou’s material given normal experimentation of Sutou’s teachings since Sutou discloses Al and Cu from 1% to 59% (paragraphs 0012, 0027-0037) and Al and Ga are both trivalent elements in Group IIIA of the periodic table sharing a lot in common, as such, would be deemed obvious substitutions under normal experimentation. Likewise with Cu and Ag, both being transition metals of Group 11 of the periodic table and both are known to be highly mobile in many chalcogenide materials and can participate in ionic/metallic switching mechanisms.
Regardaing claim 14, Sutou further discloses wherein in the step of
recording information, at least one type of crystal selected from GeTe4, GeTe, Te, and
Ga₂Te₃ is precipitated (inherent given the chemical makeup of examples such as ex 10-18, 23 given, figs. 1A-B).
Response to Arguments
Applicant’s arguments with respect to the amended claims have been considered but are moot because the new ground of rejection does not rely on any reference applied in the prior rejection of record for any teaching or matter specifically challenged in the argument.
Conclusion
Applicant's amendment necessitated the new ground(s) of rejection presented in this Office action. Accordingly, THIS ACTION IS MADE FINAL. See MPEP § 706.07(a). Applicant is reminded of the extension of time policy as set forth in 37 CFR 1.136(a).
A shortened statutory period for reply to this final action is set to expire THREE MONTHS from the mailing date of this action. In the event a first reply is filed within TWO MONTHS of the mailing date of this final action and the advisory action is not mailed until after the end of the THREE-MONTH shortened statutory period, then the shortened statutory period will expire on the date the advisory action is mailed, and any nonprovisional extension fee (37 CFR 1.17(a)) pursuant to 37 CFR 1.136(a) will be calculated from the mailing date of the advisory action. In no event, however, will the statutory period for reply expire later than SIX MONTHS from the mailing date of this final action.
Any inquiry concerning this communication or earlier communications from the examiner should be directed to DOUGLAS M MENZ whose telephone number is (571)272-1877. The examiner can normally be reached Monday-Friday 8:00am-5:00pm.
Examiner interviews are available via telephone, in-person, and video conferencing using a USPTO supplied web-based collaboration tool. To schedule an interview, applicant is encouraged to use the USPTO Automated Interview Request (AIR) at http://www.uspto.gov/interviewpractice.
If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, Jacob Choi can be reached at 469-295-9060. The fax phone number for the organization where this application or proceeding is assigned is 571-273-8300.
Information regarding the status of published or unpublished applications may be obtained from Patent Center. Unpublished application information in Patent Center is available to registered users. To file and manage patent submissions in Patent Center, visit: https://patentcenter.uspto.gov. Visit https://www.uspto.gov/patents/apply/patent-center for more information about Patent Center and https://www.uspto.gov/patents/docx for information about filing in DOCX format. For additional questions, contact the Electronic Business Center (EBC) at 866-217-9197 (toll-free). If you would like assistance from a USPTO Customer Service Representative, call 800-786-9199 (IN USA OR CANADA) or 571-272-1000.
/DOUGLAS M MENZ/Primary Examiner, Art Unit 2897 8/16/26
Chalcogenide Glasses Based On Tellurium For Transmitting Infrared In The Middle And Far Regions
PATENT NUMBER
1642870
DOCUMENT ID
EP 1642870 A1
DATE PUBLISHED
2006-04-05
INVENTOR INFORMATION
NAME
CITY
STATE
ZIP CODE
COUNTRY
DANTO SYLVAIN
N/A
N/A
N/A
FR
ZHANG XIANG HUA
N/A
N/A
N/A
FR
LUCAS JACQUES
N/A
N/A
N/A
FR
APPLICATION NO
EP 05077035 A
DATE FILED
2005-09-06
CPC CURRENT
TYPE
CPCI
CPCI
CPC
C 03 C 3/321
C 03 C 3/323
DATE
2013-01-01
2013-01-01
Abstract
Tellurium-based chalcogenide glass has a transition temperature (Tg) greater than 140o>C, a crystallisation temperature (Tx) of at least 100o>C greater than Tg, and an infrared transmission window extending from 2 to 30 mu m. INDEPENDENT CLAIM are also included for: (a) use of the chalcogenide glass for the fabrication of an optical element intended for the transmission of infrared radiation; and (b) an optical element intended for the transmission of infrared radiation.
Description
Chalcogenide glasses, used as materials for infrared transmission, are mainly represented by compositions based on sulfur or selenium, combined with other elements such as germanium, arsenic, gallium, antimony or a halogen like iodine.
Any glass intended for the production of massive optical elements, such as lenses or optical fibers, must be sufficiently stable. This stability can be expressed on one hand by the range between the temperature of vitreous transition Tg (softening) and the crystallization temperature T .sub.x (devitrification). The larger this differential, the easier the glass is to shape, for example by hot molding. On the other hand, the shape stability requires a sufficiently high glass transition temperature Tg, in particular higher than the operating temperature of the optical elements.
Several compositions of this type are registered trademarks, such as AMTIR® I glass of composition Ge .sub.33 As .sub.12 Se .sub.55 or GASIR® I glass of composition Ge .sub.22 As .sub.20 Se .sub.58 .
When the glasses are sulfur based, chalcogen pus light, they transmit infrared light up to 10 microns for thicknesses of the order of one millimeter. When the glasses are based on selenium, heavier element, the infrared transmission extends up to 14 microns.
The use of Te, a chalcogenic element that is even heavier than selenium, may therefore seem attractive for the production of transparent glasses in far-infrared light.
However, it is well known that, although sulfur and selenium readily vitrify by cooling the liquidus after the melting of the elements, molten tellurium is impossible to vitrify, even by quenching the liquidus. If there are some tellurium-based glasses, their composition is often optimized for specific applications: they do not have the qualities required for the development of massive optical elements for transmission in the far infrared.
Thus, some known tellurium-based glasses are candidates for technologies such as optical storage of information and are then called phase change materials because of the great instability of the glassy phase which can only be obtained in the form of thin layers of a few nanometers. The interest of these glasses lies in their rapid and easy transformation into crystalline phases. However, it is believed that to vitrify phase change lenses for DVD application, it is necessary to use very high quench rates, of the order of 100 million degrees per second. This type of very unstable glasses has been studied in systems such as Te / Ge / Sb, Te / Ge / In and Te / Sb / Ag / In. It is of course not usable for the manufacture of elements massive optics.
Other known compositions, such as Ge / Te / Ga or Ge / Te / In, are considered to have remarkable electronic properties because of their semiconductor nature (see Glass formation and properties of glasses in germanium-tellurium). -gallium and germanium-tellurium-indium systems, Apykhtin et al., Fizika i Khimiya Stekla (1980), 6 (4), 383-8). However, the disclosed lenses do not exhibit sufficient thermal stability for the manufacture of solid optical elements, the Tg interval T .sub.x is always less than 100 ° C. Their use is in the field of thin films and their application in infrared optics is not mentioned.
No. 3,343,972 describes Te / As / Ge glasses, rich in tellurium and arsenic, for application in infrared optics. Their optical transmission window remains however limited to 25 microns. Only ternary glasses without Ga have been made and the thermal stability is not reported.
No. 6,015,765 for its part describes Te / As / Ge glasses which may also contain Ga, I .sub.2 , Se and In, having a sufficient thermal stability for the manufacture of solid optical elements. These glasses are, however, optimized for use in optical amplification using doping elements such as rare earths. The optical transmission window remains limited to 20 μm. These glasses do not contain more than 60% of Te.
The object of the present invention is the development of a glass having an optical transmission window ranging from the near infrared to the far infrared, while offering sufficient thermal stability to consider the economically viable production of optical elements. massive.
The invention relates in particular to a Te-based chalcogenide glass, characterized by a transition temperature Tg of more than 140 ° C, a crystallization temperature T .sub.x of at least 100 ° C higher than Tg, and a infrared transmission window extending from 2 to 30 μm.
This glass is preferably composed according to the formula Gex Tey Gaz Mm ,
M representing at least one compound selected from the list Ag, Al, As, Cu, In, Sn, Zn, I .sub.2 and Pb,
x = 10-20%, y = 65 - 85%, z = 4 - 15%, m = 1 - 21%, and x + y + z + m = 100%.
Advantageously, this glass is characterized in that
x = 14 - 18%, y = 70 - 80%, z = 5 - 12%, m = 1 - 11%, and x + y + z + m = 100%.
More preferably, M represents a single compound among Ag, I .sub.2 , In, Pb, Sn, and Pbl .sub.2 , present at a maximum concentration level of 8% for Ag, 10% for I .sub.2 , 3% for In, 2% for Pb, 1% for Sn and 5% for PbI .sub.2 .
The present invention also relates to optical elements for the transmission of infrared radiation, comprising a chalcogenide glass as defined above, and the use of these glasses for the manufacture of optical elements for the transmission of infrared radiation. such as lenses or optical fibers.
The transmission window is defined here as the wavelength range for which at least 10% of the incident intensity passes through a laminar sample of a thickness of 1 mm. This parameter includes Fresnel losses, which are unavoidable when measuring a sample without antireflection layers. These losses are consistent in view of the refractive index of the material which is of the order of 3 to 3.5.
Note also that in this document all percentages are expressed as atomic percent.
The core of the invention is therefore to combine a particularly high tellurium content (more than 65%), preferably with three other elements, including germanium and gallium, in order to obtain a glass with exploitable characteristics for training massive objects. For example, a glass of very good quality is obtained by combining 71% Te, 14% Ge, 10% Ga and 5% Ag.
Table 1 groups together other examples of vitreous compositions according to the invention as well as the thermal characteristics of the glasses obtained. As a reminder, Tg is the glass transition temperature, T .sub.x the crystallization temperature and T .sub.f the melting temperature. These characteristic temperatures are measured using DSC (Differential Scanning Calorimetry) equipment. tabl0001 Composition T.sub.g(° C) T.sub.x(° C) T.sub.f(° C) T.sub.x- T.sub.g(° C) Ag .sub.5 Ga .sub.9.5 Ge .sub.14.25 Te .sub.71.25 180 294 351 114 Ag .sub.5 Ga .sub.10 Ge .sub.15 Te .sub.70 188 288 342 100 As .sub.5 Ga .sub.9.5 Ge .sub.14.25 Te .sub.71.25 171 277 346 106 (PbI .sub.2 ) .sub.5 Ga .sub.9.5 Ge .sub.14.25 Te .sub.71.25 160 * - * *: no crystallization peak -: not measured
One criterion used to evaluate the stability of glasses is the interval Tg to T .sub.x . The bigger the difference, the more stable the lenses are. We obtain values equal to or greater than 100 ° C, which is a sufficient gap to consider the preparation of massive optical objects.
The higher Tg values, corresponding to the most interesting glasses, are achieved for the ternary Ga / Ge / Te which is added a fourth element M, in particular Ag, As or PbI .sub.2. The addition of a maximum of 5% PbI .sub.2 has the effect of greatly reducing the enthalpy of crystallization, and thus greatly improve the stability of the glass.
Such glasses may be prepared according to the protocol described below, which comprises the following operations.
The necessary elements are weighed and metered, the appropriate quantities being easy to determine by those skilled in the art. The elements used must be very large purity (5N), the oxygen contamination must especially be less than 10 ppm.
To eliminate any risk of oxidation during heating, the elements are introduced into a silica assembly and the assembly is drawn under vacuum using a pump. The reaction tube containing the elements is sealed with a torch, fed for example with butane-oxygen.
The reaction tube is then placed in a tilting oven at 750 ° C for 12 hours. The molten bath is taken out of the oven and soaked in cold water. A quenching rate of the order of 100 ° C. per second is adequate.
A critical cooling rate of only a few tens of degrees per second makes it possible to obtain samples of the order of one centimeter in thickness without crystallization in the mass.
To improve the mechanical properties of the glasses obtained after quenching, the samples are annealed for 2 hours at a temperature of Tg - 20 ° C.
Table 2 gives other examples of compositions according to the invention. tabl0002 Ge You Ga M = Ag 15 75 5 5 14.25 71.25 9.5 5 10 75 10 5 15 70 10 5 10 70 15 5 Ge You ga M = As 14.25 71.25 9.5 5 15 70 10 5 15 75 5 5 10 80 5 5 Ge You ga M = PbI.sub.2 14.25 71.25 9.5 5 15 70 10 5 15 75 5 5
Claims
Chalcogenide glass based on Te, characterized by a transition temperature Tg of more than 140 ° C, by a crystallization temperature T .sub.x at least 100 ° C higher than Tg, as well as by an infrared transmission window extending from 2 to 30 μm.
Chalcogenide glass according to Claim 1, characterized by the formula Ge .sub.x Te .sub.y Ga .sub.z M .sub.m ,
M representing at least one compound selected from the list Ag, Al, As, Cu, I .sub.2 , In, Pb, Sn, Zn and PbI .sub.2 , with
x = 10 to 20%, y = 65 to 85%, z = 4 to 15%, m = 1 to 21%, and x + y + z + m = 100%.
Chalcogenide glass according to claim 2, characterized in that
x = 14 to 18%, y = 70 to 80%, z = 5 to 12%, and m = 1 to 11%.
A chalcogenide glass according to claim 2 or 3, wherein M is one of Ag, I .sub.2 , In, Pb, Sn, and PbI .sub.2 , present at a concentration level of at most 8% for Ag, 10% for I .sub.2 , 3% for In, 2% for Pb, 1% for Sn and 5% for PbI .sub.2 .
Use of a chalcogenide glass according to any one of claims 1 to 4 for the manufacture of an optical element for the transmission of infrared radiation.
An optical element for transmitting infrared radiation, comprising a chalcogenide glass according to any one of claims 1 to 4.
Optical element according to Claim 6, characterized in that it consists of a lens or an optical fiber.
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