Abstract:
Monomers containing two or more hexafluoroisopropyl groups and containing plural saturated rings are polymerized to form polymers of high transparency optical properties at 157 nm wavelengths and improved etch resistance compared to polymers formed from single ring monomers.

Description:
TECHNICAL FIELD  
         [0001]    The invention is directed to monomers, which are polymerizable to form photoresists for 157 nm lithography.  
         BACKGROUND OF THE INVENTION  
         [0002]    Optical lithography at 248 nm or 193 nm wavelengths requires resolution enhancement techniques for high resolution small feature sizes for integrated circuits.  
           [0003]    Use of shorter exposure wavelengths to avoid complexities involved in resolution enhancement techniques, is now being considered.  
           [0004]    With recent improvements in laser technology and optical materials, optical lithography at 157 nm using an F 2  excimer laser light source has emerged as the current choice for post-193-nm technology in the fabrication of devices with features sizes less than 100 nm.  
           [0005]    A single-layer photoresist process for imaging at 157 nm is favored among potential industry consumers.  
           [0006]    Potential materials for use in a single layer photoresist must offer high transparency at exposure wavelength, resistance to plasma etching processes, and the ability to undergo efficient photochemical transformations that change their solubility in developer solution.  
           [0007]    It has been previously discovered that structures containing two or more hexafluoroisopropyl (HFIP) groups can be used to functionialize methacrylate, acrylate and styrenic monomers and that the functionalized monomers will form polymers of low optical absorbance at 157 nm wavelengths. This was reported in Bae, Y. C., et al, Polymer Preprints 42 (2), 403-404 (2001) and Bae, Y. C., et al, Chem. Mater. 14, 1306-1313 (Jan. 31, 2002) where the syntheses are disclosed of 2-[4-(2-hydroxyhexafluoroisopropyl)cyclohexane]hexafluoroisopropyl acrylate, 2-[4-(2,2,2-trifluoro-1-methoxymethoxy-1-trifluoromethylethyl)cyclohexane]hexafluoroisopropyl acrylate and 2-[4-(2,2,2-trifluoro-1-ethoxymethoxy-1-trifluoromethylethyl)] styrene. These materials have limited etch resistance.  
         SUMMARY OF THE INVENTION  
         [0008]    It has been discovered herein that monomers can be prepared that can be polymerized to form polymers of similar high transparency optical properties at 157 nm wavelengths and improved etch resistance. It has been discovered that by a unique combination of elements providing such monomers comprise 2 or more hexafluoroisopropyl (HFIP) groups and 2 or more rings.  
           [0009]    One embodiment of the invention herein that meets such advantage, denoted the first embodiment, is a composition having the structure  
                         
 
           [0010]    where n is 0, 1 or 2, R 1  is selected from the group consisting of cyclohexylene, cyclohexyl ether and hexafluoroisopropyl cyclohexyl or is not present and R 2  is selected from the group consisting of hydrogen, fluorine and chlorine atoms and methyl and trifluoromethyl groups, with the proviso that when n=0, the structure (I) contains at least two rings; or a composition having the structure  
                         
 
           [0011]    where R 1  and R 2  are as defined previously and Q is selected from the group consisting of  
                         
 
           [0012]    Another embodiment of the invention herein, denoted the second embodiment, is directed to composition having the structure  
                         
 
           [0013]    where n is 0, 1 or 2, R 1  is selected from the group consisting of cyclohexylene, cyclohexyl ether and hexafluoroisopropyl cyclohexyl or is not present and R 3  is CO or is not present; or a composition having the structure  
                         
 
           [0014]    where R 1  and R 3  are as defined previously and Q is selected from the group consisting of  
                         
 
           [0015]    Starting materials for structures (Ib), (Ic), (Id), (Ie), (XIb), (XIc), (XId) and (XIe) are commercially available or given this disclosure can be synthesized by those skilled in the art.  
           [0016]    For the first and second embodiments when R 1  is cyclohexyl ether, the ether group can attach to any carbon in the ring to which it is shown bonding to, which is not a bridgehead carbon.  
           [0017]    For the first and second embodiments for the cases with Q, R 1  and hexafluoroisopropyl moiety can attach to any carbon in the ring to which it is shown bonding to, which is not a bridgehead carbon.  
           [0018]    Another embodiment herein, denoted the third embodiment is directed at low absorbing polymer at 157 nm wavelengths having the structure  
                         
 
           [0019]    where n ranges from 4 to 30.  
           [0020]    As used herein, the term methyl means —CH 3 .  
           [0021]    As used herein, the term “trifluoromethyl” means —CF 3 .  
           [0022]    As used herein, the terms “low absorbance” and “low-optical absorbance” both mean the same and mean absorbance at 157 nm at less than 3.00 μm −1 .  
           [0023]    As used herein, the term “high transparency optical properties at 157 nm wavelengths” means absorbing at 157 nm at less than 3.00 μm −1 .  
         DETAILED DESCRIPTION  
         [0024]    We turn now to the first embodiment herein, that is compounds of the structure (I) as described above.  
           [0025]    In general these compounds are made by starting with plural unsaturated ring precursors, e.g., containing biphenyl or naphthalene or anthracene moieties and two or more hexafluoroisopropyl groups and hydroxy group on hexafluoroisopropyl (HFIP) group, and hydrogenating, e.g., using a supported rhodium catalyst, to form aliphatic low absorbance ring groups coupled to the HFIP groups and then reacting hydroxy with acryloyl, methacryloyl, α-trifluoromethyl acryloyl, 2-fluoroacryloyl or 2-chloroacryloyl chloride in tetrahydrofuran or dichloromethane, and hydrolyzing by the addition of water.  
           [0026]    A subgenus of these compounds where R 1  is cyclohexyl ether, has the structure  
                         
 
           [0027]    where R 2  is selected from the group consisting of hydrogen, fluorine and chlorine atoms and methyl and trifluoromethyl groups. The starting material for these compounds is 4,4′-bis(2-hydroxyhexafluoroisopropyl) diphenyl ether (which is commercially available), which is hydrogenated to produce 1,1,1,3,3,3-hexafluoro-2-{4-[-(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-cyclohexyloxy]cyclohexyl}-propan-2-ol, which is reacted with acryloyl chloride or substituted acryloyl chloride, followed by hydrolysis, to produce a compound (II).  
           [0028]    One compound of the subgenus (II) has the structure  
                         
 
           [0029]    This compound is prepared in working Example I hereinafter.  
           [0030]    A subgenus of the compound (I) where R 1  is cyclohexyl, has the structure  
                         
 
           [0031]    where R 2  is selected from the group consisting of hydrogen, fluorine and chlorine atoms and methyl and trifluoromethyl groups. A hydrogenation product starting material for producing compounds (IV) is 1,1,1,3,3,3-hexafluoro-2-[4′-(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-bicyclohexyl-4-yl]-propan-2-ol which is reacted with acryloyl chloride or substituted acryloyl chloride, followed by hydrolysis, to produce a compound (IV). The hydrogenation product starting material is made from the commercially available starting material 4,4′-bis(2-hydroxyhexafluoroisopropyl)diphenyl by hydrogenation as described in working Example I.  
           [0032]    One compound of subgenus (IV) has the structure  
                         
 
           [0033]    This compound is prepared in working Example II hereinafter.  
           [0034]    A subgenus of the compounds (I) where R 1  is hexafluoroisopropyl cyclohexyl has the structure  
                         
 
           [0035]    where R 2  is selected from the group consisting of hydrogen, fluorine and chlorine atoms and methyl and trifluoromethyl groups. A hydrogenation product starting material for producing compounds (VI) is 1,1,1,3,3,3-hexafluoro-2-[4′-{2,2,2-trifluoro-1-[4-(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-cyclohexyl]-1-trifluoromethyl ethyl}-cyclohexyl]-propan-2-ol which is reacted with acryloyl chloride or substituted acryloyl chloride, followed by hydrolysis, to produce a compound (VI). The hydrogenation product starting material is made from the commercially available starting material 1,1,1,3,3,3-hexafluoro-2-[4′-{2,2,2-trifluoro-1-[4-(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)phenyl]-1-trifluoromethyl-ethyl}-phenyl]-propan-2-ol by hydrogenation as described in working Example I.  
           [0036]    One compound of subgenus (VI) has the structure  
                         
 
           [0037]    This compound is prepared in working Example III hereinafter.  
           [0038]    A subgenus of the compounds (I) where R 1  is not present and n=1 has the structure  
                         
 
           [0039]    where R 2  is selected from the group consisting of hydrogen, fluorine and chlorine atoms and methyl and trifluoromethyl groups. A hydrogenation product starting material for producing compounds (VIII) is 1,1,1,3,3,3-hexafluoro-2-[6-(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-decahydro-naphthalen-2-yl]-propan-2-ol which is reacted with acryloyl chloride or substituted acryloyl chloride, followed by hydrolysis, to produce a compound (VIII). The hydrogenation product starting material is made from the starting material 1,1,1,3,3,3-hexafluoro-2-[6-(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-naphthalen-2-yl]-propan-2-ol by hydrogenation as described in working Example I. The starting material which is subjected to hydrogenation is prepared from the commercially available starting materials 2,6-dibromonaphthalene and hexafluoroacetone under Grignard Reaction conditions to give the corresponding tertiary alcohol.  
           [0040]    One compound of subgenus (VIII) has the structure  
                         
 
           [0041]    This compound is prepared in working example IV hereinafter.  
           [0042]    A subgenus of the compound (I) where R 1  is not present and n=2 has the structure  
                         
 
           [0043]    where R 2  is selected from the group consisting of hydrogen, fluorine and chlorine atoms and methyl and trifluoromethyl groups. A hydrogenation product starting material for producing compounds (X) is 1,1,1,3,3,3-hexafluoro-2-[6-(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-tetradecahydro-anthracen-2-yl]-propan-2-ol which is reacted with acryloyl chloride or substituted acryloyl chloride, followed by hydrolysis, to produce a compound (X). The hydrogenation product starting material is made from the starting material 1,1,1,3,3,3-hexafluoro-2-[6-(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-anthracene-2-yl]-propan-2-ol by hydrogenation as described in working Example I. Thee starting material which is subjected to hydrogenation is prepared from the commercially available starting materials 2,6-dibromoanthracene and hexafluoroacetone under Grignard Reaction conditions to give the corresponding tertiary alcohol.  
           [0044]    The compounds (I) can be polymerized to form polymers of low optical absorbance at 157 nm wavelengths and good etch resistance in the presence of a catalyst for vinyl polymerization, e.g., 2,2′-azobisisobutyronitrile (AIBN) in tetrahydrofuran (THF) e.g., at 60-70° C.  
           [0045]    We turn now to the second embodiment herein, that is compounds of the structure (XI) as described above.  
           [0046]    In general, compounds (XI), where R 3  is CO, are made starting with unsaturated ring precursor and two or more hexafluoroisopropyl groups and hydroxy group on hexafluoroisopropyl (HFIP) group, and hydrogenating, e.g., using a supported rhodium catalyst, to form aliphatic low absorbance ring group(s) coupled to HFIP groups and then reacting hydrogenation product, e.g., hydrogenated diol, with bicyclo[2.2.1]hept-5-ene-2-carbonyl chloride in the presence of n-butyllithium in tetrahydrofuran and hydrolyzing by the addition of water, to replace hydrogen on hydroxy with bicyclo[2.2.1]hept-5-ene-2-carbonyl.  
           [0047]    In general compounds (XI) where R 3  is not present are made as described in the above paragraph except substituting 5-chlorobicyclo[2.2.1]hept-2-ene for the bicyclo[2.2.2]hept-5-ene-2-carbonyl chloride.  
           [0048]    One compound embraced by genus (XI), where R 3  is CO and R 1  is not present and n=0, has the structure  
                         
 
           [0049]    A hydrogenation product starting material for producing compound (XII) is 1,1,1,3,3,3-hexafluoro-2-[3-(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-cyclohexyl]-propan-2-ol, which is reacted with bicyclo[2.2.1]hept-5-ene-2-carbonyl chloride in the presence of butyllithuim in tetrahydrofuran, followed by hydrolysis by addition of water, to produce compound (XII). The hydrogenation product starting material is made from the commercially available starting material 1,1,1,3,3,3-hexafluoro-2-[3-(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-phenyl]-propan-2-ol by hydrogenation as described in working Example I. The compound (XII) is prepared in working Example XXVI hereinafter.  
           [0050]    Another compound embraced by genus (XI), where R 3  is CO and R 1  is not present and n=1, has the structure  
                         
 
           [0051]    A hydrogenation product starting material for producing compound (XIII) is 1,1,1,3,3,3-hexafluoro-[6-(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-decahydro-naphthalen-2-yl]-propan-2-ol which is reacted with bicyclo[2.2.1]hept-5-ene-2-carbonyl chloride in the presence of n-butyllithium in tetrahydrofuran, followed by hydrolysis by the addition of water, to produce compound (XIII). The hydrogenation product starting material is made from the same commercially available starting materials as compounds (VIII) by hydrogenation as described in working Example I. The compound (XIII) is prepared in working Example XXVII hereinafter.  
           [0052]    Still another compound embraced by genus (XI), where R 3  is CO and R 1  is not present and n=2, has the structure  
                         
 
           [0053]    A hydrogenation product starting material for producing compound (XIV) is 1,1,1,3,3,3-hexafluoro-2-[6-(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-tetradecahydro-anthracen-2-yl]-propan-2-ol which is reacted with bicyclo[2.2.1]hept-5-ene-2-carbonyl chloride in the presence of n-butyllithium in tetrahydrofuran, followed by hydrolysis by the addition of water, to produce compound (XIV). The hydrogenation product starting material is made from the same commercially available starting materials as compounds (X) by hydrogenation as described in working Example I. The compound (XIV) is prepared in working Example XXVIII hereinafter.  
           [0054]    Yet another compound embraced by genus (XI), where R 3  is CO, R 1  is cyclohexyl ether and n=0, has the structure  
                         
 
           [0055]    Hydrogenation product starting material for producing compound (XVIII) is 1,1,1,3,3,3-hexafluoro-2-{4′-[-(2,2,2-trifluoro-1-hydroxy-1-trifluoromethylethyl)-cyclohexyloxy]cyclohexyl}-propan-2-ol which is reacted with bicyclo[2.2.1]hept-5-ene-2-carbonyl chloride in the presence of n-butyllithium in tetrahydrofuran, followed by hydrolysis by the addition of water, to produce compound (XVIII). The hydrogenation product starting material is made as described in working Example I. The compound (XVIII) is prepared in working Example XXIX hereinafter.  
           [0056]    Yet another compound embraced by genus (XI), where R 3  is CO and R 1  is cyclohexyl and n=0, has the structure  
                         
 
           [0057]    A hydrogenation product starting material for producing compound (XV) is 1,1,1,3,3,3-hexafluoro-2-[4′-(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-bicylohexyl-4-yl]-propan-2-ol which is reacted with bicyclo[2.2.1]hept-5-ene-2-carbonyl chloride in the presence of n-butyllithium in tetrahydrofuran, followed by hydrolysis by the addition of water, to produce compound (XV). The hydrogenation product starting material is made from the same commercially available starting materials as compounds (IV) by hydrogenating as described in working Example I. The compound is prepared in working Example XXX hereinafter.  
           [0058]    Yet another compound embraced by genus (XI), where R 3  is CO, R 1  is hexafluoroisopropyl cyclohexyl and n=0, has the structure  
                         
 
           [0059]    Hydrogenation product starting material for producing compound (XVI) is 1,1,1,3,3,3-hexafluoro-2-[4′-{2,2,2-trifluoro-1-[4-(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-cyclohexyl]-1-trifluoromethyl-ethyl}-cyclohexyl]-propan-2-ol which is reacted with bicyclo[2.2.1]hept-5-ene-2-carbonyl chloride in the presence of n-butyllithium in tetrahydrofuran, followed by hydrolysis by the addition of water, to produce compound (XVI). The hydrogenation product starting material is made from the same starting material as compounds (VI) by hydrogenation as described in working Example I. The compound (XVI) is prepared in working Example XXXI hereinafter.  
           [0060]    The compounds (XI) are polymerized to form low absorbing polymers at 157 nm wavelengths by metal-catalyzed polymerization. The norbornene ring does not open on polymerization but becomes saturated and joins another ring monomer which becomes saturated.  
           [0061]    We turn now to the third embodiment herein, that is the low absorbing polymer at 157 nm wavelength having the structure  
                         
 
           [0062]    where n ranges from 4 to 30. This is prepared by polymerizing compound (III) in the presence of 2,2′-azobisisobutyronitrile in tetrahydrofuran at 60-70° C. A polymer (XVII) where n=7 is prepared in working Example XXXIII hereinafter.  
           [0063]    Imaging at 157 nm can be carried out using an Exitech 157 nm Microstepper (NA=0.6, σ=0.7). Polymers are dissolved in propylene glycol methyl ether acetate (PGMEA). The resist solution is filtered through a 0.2 μm membrane filter and spin-coated onto silicon wafers that are either primed with HMDS gas or treated with anti-reflective coatings. Post-apply bake and post-exposure bake can be carried out at 90-130° C. and development can be conducted in 0.262 N tetramethyl ammonium hydroxide solution.  
           [0064]    Absorbance at 157 nm can be recorded on a VU-301 vacuum ultraviolet variable angle spectroscopic ellipsometer (VUV-VASE) instrument.  
           [0065]    Etch resistance can be measured by using a Plasma Therm 72 RIE system which is a 10-inch diameter parallel plate, molecular turbo-pumped system which is microprocessor controlled and gives 5% uniformity and applies fluorine based plasma including CHF 3 , SF 6  and CF 4  for anisotropic etching of silicon, silicon dioxide and silicon nitride and operates at 10-1000 um processing pressure.  
           [0066]    The invention is illustrated by the following working examples. 
       
    
    
     EXAMPLE I  
     Synthesis of Compound (III)  
       [0067]    1,1,1,3,3,3-Hexafluoro-2-{4′-[-(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-cyclohexyloxy]cyclohexyl}-propan-2-ol was prepared by hydrogenation of 4,4′-bis(2-hydroxyhexafluoroisopropyl)diphenyl ether using a supported rhodium catalyst (5 wt % on carbon powder). Using this Scheme, 47% yield was obtained on the basis of diol and the separated products by column chromatography included 52.2 mol % of monoacrylate, 15.5 mol % of diacrylate and 32.3 mol % of diol. To a solution of 1,1,1,3,3,3-hexafluoro-2{4′-[-2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-cyclohexyloxyl}cyclohexyl}-propan-2-ol (5 g, 0.0097 mol) in dry tetrahydrofuran (THF), was added 6.1 mL of 1.6 M n-butyllithium (0.0097 mol) under nitrogen during 30 minutes by dropwise addition of acryloyl chloride (0.88 g, 0.0097 mol) dissolved in dry THF. The resulting solution was stirred overnight at room temperature and hydrolyzed by the addition of distilled water. The aqueous phase was extracted with ethyl ether, and the combined organic phase was dried over MgSO 4 . The crude product was purified by column chromatography (49% yield).  1 H NMR (CDCl 3 , 400 MHz) δ 6.51(1H, CHH trans ═CH—), 6.12 (1H, CH 2 —CH—), 5.98(CHH cis ═CH—), 3.6 (1H, methine H, adjacent to ester), 3.2 (2H, methine H, adjacent to ether), 3.0-3.1 (1H, methine H, adjacent to hydroxyl and 1H, —OH), 1.2-2.1 (methylene H in the rings).  
       EXAMPLE II  
     Synthesis of Compound V  
       [0068]    To a solution of 1,1,1,3,3,3-hexafluoro-2-[4′-(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-bicyclohexyl-4-yl]-propan-2-ol in dry THF, is added n-butyllithium (1 equivalent) under nitrogen during 30 minutes followed by dropwise addition of acryloyl chloride (1 equivalent) dissolved in dry THF. The resulting solution is stirred overnight at room temperature and hydrolyzed by the addition of distilled water. The aqueous phase is extracted with ethyl ether, and the combined organic phase is dried over MgSO 4 . The crude product is purified by column chromatography.  
       EXAMPLE III  
     Synthesis of Compound (VII)  
       [0069]    To a solution of 1,1,1,3,3,3-hexafluoro-2-[4′-{2,2,2-trifluoro-1-[4-(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-cyclohexyl]-1-trifluoromethyl-ethyl}-cyclohexyl]-propan-2-ol in dry THF, is added n-butyllithium (1 equivalent) under nitrogen during 30 minutes followed by dropwise addition of acryloyl chloride (1 equivalent) dissolved in dry THF. The resulting solution is stirred overnight at room temperature and hydrolyzed by the addition of distilled water. The aqueous phase is extracted with ethyl ether, and the combined organic phase is dried over MgSO 4 . The crude product is purified by column chromatography.  
       EXAMPLE IV  
     Synthesis of Compound (IX)  
       [0070]    To a solution of 1,1,1,3,3,3-hexafluoro-2-[6-(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-decahydro-naphthalen-2-yl]-propan-2-ol in dry THF, is added n-butyllithium (1 equivalent) under nitrogen during 30 minutes followed by dropwise addition of acryloyl chloride (1 equivalent) dissolved in dry THF. The resulting solution is stirred overnight at room temperature and hydrolyzed by the addition of distilled water. The aqueous phase is extracted with ethyl ether, and the combined organic phase is dried over MgSO 4 . The crude product is purified by column chromatography.  
       EXAMPLE V  
     Synthesis of Compound (VIII) Where R 2  is Methyl  
       [0071]    To a solution of 1,1,1,3,3,3-hexafluoro-2-[6-(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-decahydro-naphthalen-2-yl]-propan-2-ol in dry THF, is added n-butyllithium (1 equivalent) under nitrogen during 30 minutes followed by dropwise addition of methacryloyl chloride (1 equivalent) dissolved in dry THF. The resulting solution is stirred overnight at room temperature and hydrolyzed by the addition of distilled water. The aqueous phase is extracted with ethyl ether, and the combined organic phase is dried over MgSO 4 . The crude product is purified by column chromatography.  
       EXAMPLE VI  
     Synthesis of Compound (VIII) Where R 2  is Trifluoromethyl  
       [0072]    To a solution of 1,1,1,3,3,3-hexafluoro-2-[6-(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-decahydro-naphthalen-2-yl]-propan-2-ol in dry dichloromethane (DCM) is added 1 equivalent of freshly distilled triethylamine (in dry DCM) under nitrogen over a period of 30 min at 0° C. After 1 h, the resulting solution is treated with 2.4 g of α-trifluoromethyl acryloyl chloride dissolved in 5 mL dry DCM over 30 min at 0° C. The resulting solution is stirred overnight at room temperature and hydrolyzed by the addition of 50 mL of distilled water. The aqueous phase is extracted with ethyl ether and the combined organic phase is dried over MgSO 4 . The crude product is purified by column chromatography.  
       EXAMPLE VII  
     Synthesis of Compound (VIII) Where R 2  is a Fluorine Atom  
       [0073]    To a solution of 1,1,1,3,3,3-hexafluoro-2-[6-(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-decahydro-naphthalen-2-yl]-propan-2-ol in dry dichloromethane (DCM) is added 1 equivalent of freshly distilled triethylamine (in dry DCM) under nitrogen over a period of 30 min at 0° C. After 1 h, the resulting solution is treated with 2.4 g of fluoroacryloyl chloride dissolved in 5 mL dry DCM over 30 min at 0° C. The resulting solution is stirred overnight at room temperature and hydrolyzed by the addition of 50 mL of distilled water. The aqueous phase is extracted with ethyl ether and the combined organic phase is dried over MgSO 4 . The crude product is purified by column chromatography.  
       EXAMPLE VIII  
     Synthesis of Compound (VIII) Where R 7  is a Chlorine Atom  
       [0074]    To a solution of 1,1,1,3,3,3-hexafluoro-2-[6-(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-decahydro-naphthalen-2-yl]-propan-2-ol in dry dichloromethane (DCM) is added 1 equivalent of freshly distilled triethylamine (in dry DCM) under nitrogen over a period of 30 min at 0° C. After 1 h, the resulting solution is treated with 2.4 g of 2-chloroacryloyl chloride dissolved in 5 mL dry DCM over 30 min at 0° C. The resulting solution is stirred overnight at room temperature and hydrolyzed by the addition of 50 mL of distilled water. The aqueous phase is extracted with ethyl ether and the combined organic phase is dried over MgSO 4 . The crude product is purified by column chromatography.  
       EXAMPLE IX  
     Synthesis of Compound (X) Where R 2  is a Hydrogen Atom  
       [0075]    To a solution of 1,1,1,3,3,3-hexafluoro-2-[6-(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-tetradecahydro-anthracen-2-yl]-propan-2-ol in THF, is added n-butyllithium (1 equivalent) under nitrogen during 30 minutes followed by dropwise addition of acryloyl chloride (1 equivalent) dissolved in dry THF. The resulting solution is stirred overnight at room temperature and hydrolyzed by the addition of distilled water. The aqueous phase is extracted with ethyl ether and the combined organic phase is dried over MgSO 4 . The crude product is purified by column chromatography.  
       EXAMPLE X  
     Synthesis of Compound (X) Where R 2  is a Methyl  
       [0076]    To a solution of 1,1,1,3,3,3-hexafluoro-2-[6-(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-tetradecahydro-anthracen-2-yl]-propan-2-ol in dry THF, is added n-butyllithium (1 equivalent) under nitrogen during 30 minutes followed by dropwise addition of methacryloyl chloride (1 equivalent) dissolved in dry THF. The resulting solution is stirred overnight at rom temperature and hydrolyzed by the addition of distilled water. The aqueous phase is extracted with ethyl ether and the combined organic phase is dried over MgSO 4 . The crude product is purified by column chromatography.  
       EXAMPLE XI  
     Synthesis of Compound (X) Where R 2  is a Trifluoromethyl  
       [0077]    To a solution of 1,1,1,3,3,3-hexafluoro-2-[6-(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-tetradecahydro-anthracen-2-yl]-propan-2-ol in dry dichloromethane (DCM) is added 1 equivalent of freshly distilled triethylamine (in dry DCM) under nitrogen over a period of 30 minutes at 0° C. After 1 h, the resulting solution is treated with 2.4 g of α-trifluoromethyl acryloyl chloride dissolved in 5 mL dry DCM over 30 min at 0° C. The resulting solution is stirred overnight at room temperature and hydrolyzed by the addition of 50 mL of distilled water. The aqueous phase is extracted with ethyl ether and the combined organic phase is dried over MgSO 4 . The crude product is purified by column chromatography.  
       EXAMPLE XII  
     Synthesis of Compound (X) Where R 2  is a Fluorine Atom  
       [0078]    To a solution of 1,1,1,3,3,3-hexafluoro-2-[6-(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-tetradecahydro-anthracen-2-yl]-propan-2-ol in dry dichloromethane (DCM) is added 1 equivalent of freshly distilled triethylamine (in dry DCM) under nitrogen over a period of 30 minutes at 0° C. After 1 h, the resulting solution is treated with 2.4 g of 2-fluoroacryloyl chloride dissolved in 5 mL dry DCM over 30 min at 0° C. The resulting solution is stirred overnight at room temperature and hydrolyzed by the addition of 50 mL of distilled water. The aqueous phase is extracted with ethyl ether and the combined organic phase is dried over MgSO 4 . The crude product is purified by column chromatography.  
       EXAMPLE XIII  
     Synthesis of Compound (X) Where R 2  is a Chlorine Atom  
       [0079]    To a solution of 1,1,1,3,3,3-hexafluoro-2-[6-(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-tetradecahydro-anthracen-2-yl]-propan-2-ol in dry dichloromethane (DCM) is added 1 equivalent of freshly distilled triethylamine (in dry DCM) under nitrogen over a period of 30 minutes at 0° C. After 1 h, the resulting solution is treated with 2.4 g of chloroacryloyl chloride dissolved in 5 mL dry DCM over 30 min at 0° C. The resulting solution is stirred overnight at room temperature and hydrolyzed by the addition of 50 mL of distilled water. The aqueous phase is extracted with ethyl ether and the combined organic phase is dried over MgSO 4 . The crude product is purified by column chromatography.  
       EXAMPLE XIV  
     Synthesis of Compound (IV) Where R 2  is Methyl  
       [0080]    To a solution of 1,1,1,3,3,3-hexafluoro-2-[4′-(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-bicyclohexyl-4-yl]-propan-2-ol in dry THF, is added n-butyllithium (1 equivalent) under nitrogen during 30 minutes followed by dropwise addition of methacryloyl chloride (1 equivalent) dissolved in dry THF. The resulting solution is stirred overnight at room temperature and hydrolyzed by the addition of distilled water. The aqueous phase is extracted with ethyl ether and the combined organic phase is dried over MgSO 4 . The crude product is purified by column chromatography.  
       EXAMPLE XV  
     Synthesis of Compound (IV) Where R 2  is Trifluoromethyl  
       [0081]    To a solution of 1,1,1,3,3,3-hexafluoro-2-[4′-(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-bicyclohexyl-4-yl]-propan-2-ol in dry dichloromethane (DCM) is added 1 equivalent of freshly distilled triethylamine (in dry DCM) under nitrogen over a period of 30 min at 0° C. After 1 h, the resulting solution is treated with 2.4 g of α-trifluoromethyl acryloyl chloride dissolved in 5 mL dry DCM over 30 min at 0° C. The resulting solution is stirred overnight at room temperature and hydrolyzed by the addition of 50 mL of distilled water. The aqueous phase is extracted with ethyl ether and the combined organic phase is dried over MgSO 4 . The crude product is purified by column chromatography.  
       EXAMPLE XVI  
     Synthesis of Compound (IV) Where R 2  is Fluorine Atom  
       [0082]    To a solution of 1,1,1,3,3,3-hexafluoro-2-[4′-(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-bicyclohexyl-4-yl]-propan-2-ol in dry dichloromethane (DCM) is added 1 equivalent of freshly distilled triethylamine (in dry DCM) under nitrogen over a period of 30 min at 0° C. After 1 h, the resulting solution is treated with 2.4 g of fluoroacryloyl chloride dissolved in 5 mL dry DCM over 30 min at 0° C. The resulting solution is stirred overnight at room temperature and hydrolyzed by the addition of 50 mL of distilled water. The aqueous phase is extracted with ethyl ether and the combined organic phase is dried over MgSO 4 . The crude product is purified by column chromatography.  
       EXAMPLE XVII  
     Synthesis of Compound (IV) Where R 2  is Chlorine Atom  
       [0083]    To a solution of 1,1,1,3,3,3-hexafluoro-2-[4′-(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-bicyclohexyl-4-yl]-propan-2-ol in dry dichloromethane (DCM) is added 1 equivalent of freshly distilled triethylamine (in dry DCM) under nitrogen over a period of 30 min at 0° C. After 1 h, the resulting solution is treated with 2.4 g of chloroacryloyl chloride dissolved in 5 mL dry DCM over 30 min at 0° C. The resulting solution is stirred overnight at room temperature and hydrolyzed by the addition of 50 mL of distilled water. The aqueous phase is extracted with ethyl ether and the combined organic phase is dried over MgSO 4 . The crude product is purified by column chromatography.  
       EXAMPLE XVIII  
     Synthesis of Compound (II) Where R 2  is Methyl  
       [0084]    To a solution of 1,1,1,3,3,3-hexafluoro-2-{4′-[(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-cyclohexyloxy]cyclohexyl}-propan-2-ol in dry THF, is added n-butyllithium (1 equivalent) under nitrogen during 30 minutes followed by dropwise addition of methacryloyl chloride (1 equivalent) dissolved in dry THF. The resulting solution is stirred overnight at room temperature and hydrolyzed by the addition of distilled water. The aqueous phase is extracted with ethyl ether, and the combined organic phase is dried over MgSO 4 . The crude product is purified by column chromatography.  
       EXAMPLE XIX  
     Synthesis of Compound (II) Where R 2  is Trifluoromethyl  
       [0085]    To a solution of 1,1,1,3,3,3-hexafluoro-2-{4′-[(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-cyclohexyloxy]cyclohexyl}-propan-2-ol in dry dichloromethane (DCM) is added 1 equivalent of freshly distilled triethylamine (in dry DCM) under nitrogen over a period of 30 min at 0° C. After 1 h, the resulting solution is treated with 2.4 g of α-trifluoromethyl acryloyl chloride dissolved in 5 mL dry DCM over 30 min at 0° C. The resulting solution is stirred overnight at room temperature and hydrolyzed by the addition of 50 mL of distilled water. The aqueous phase is extracted with ethyl ether and the combined organic phase is dried over MgSO 4 . The crude product is purified by column chromatography.  
       EXAMPLE XX  
     Synthesis of Compound (II) Where R 2  is a Fluorine Atom  
       [0086]    To a solution of 1,1,1,3,3,3-hexafluoro-2-{4′-[(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-cyclohexyloxy]cyclohexyl}-propan-2-ol in dry dichloromethane (DCM) is added 1 equivalent of freshly distilled triethylamine (in dry DCM) under nitrogen over a period of 30 min at 0° C. After 1 h, the resulting solution is treated with 2.4 g of fluoroacryloyl chloride dissolved in 5 mL dry DCM over 30 min at 0° C. The resulting solution is stirred overnight at room temperature and hydrolyzed by the addition of 50 mL of distilled water. The aqueous phase is extracted with ethyl ether and the combined organic phase is dried over MgSO 4 . The crude product is purified by column chromatography.  
       EXAMPLE XXI  
     Synthesis of Compound (II) Where R 2  is a Chlorine Atom  
       [0087]    To a solution of 1,1,1,3,3,3-hexafluoro-2-{4′-[(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-cyclohexyloxy]cyclohexyl}-propan-2-ol in dry dichloromethane (DCM) is added 1 equivalent of freshly distilled triethylamine (in dry DCM) under nitrogen over a period of 30 min at 0° C. After 1 h, the resulting solution is treated with 2.4 g of chloroacryloyl chloride dissolved in 5 mL dry DCM over 30 min at 0° C. The resulting solution is stirred overnight at room temperature and hydrolyzed by the addition of 50 mL of distilled water. The aqueous phase is extracted with ethyl ether and the combined organic phase is dried over MgSO 4 . The crude product is purified by column chromatography.  
       EXAMPLE XXII  
     Synthesis of Compound (VI) Where R 2  is Methyl  
       [0088]    To a solution of 1,1,1,3,3,3-hexafluoro-2-[4′-{2,2,2-trifluoro-1-[4-(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-cyclohexyl]-1-trifluoromethyl-ethyl}-cyclohexyl]-propan-2-ol in dry THF, is added n-butyllithium (1 equivalent) under nitrogen during 30 minutes followed by dropwise addition of methacryloyl chloride (1 equivalent) dissolved in dry THF. The resulting solution is stirred overnight at room temperature and hydrolyzed by the addition of distilled water. The aqueous phase is extracted with ethyl ether, and the combined organic phase is dried over MgSO 4 . The crude product is purified by column chromatography.  
       EXAMPLE XXIII  
     Synthesis of Compound (VI) Where R 2  is Trifluoromethyl  
       [0089]    To a solution of 1,1,1,3,3,3-hexafluoro-2-[4′-{2,2,2-trifluoro-1-[4-(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-cyclohexyl]-1-trifluoromethyl-ethyl}-cyclohexyl]-propan-2-ol in dry dichloromethane (DCM) is added 1 equivalent of freshly distilled triethylamine (in dry DCM) under nitrogen over a period of 30 min at 0° C. After 1 h, the resulting solution is treated with 2.4 g of α-trifluoromethyl acryloyl chloride dissolved in 5 mL dry DCM over 30 min at 0° C. The resulting solution is stirred overnight at room temperature and hydrolyzed by the addition of 50 mL of distilled water. The aqueous phase is extracted with ethyl ether and the combined organic phase is dried over MgSO 4 . The crude product is purified by column chromatography.  
       EXAMPLE XXIV  
     Synthesis of Compound (VI) Where R 2  is a Fluorine Atom  
       [0090]    To a solution of 1,1,1,3,3,3-hexafluoro-2-[4′-{2,2,2-trifluoro-1-[4-(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-cyclohexyl]-1-trifluoromethyl-ethyl}-cyclohexyl]-propan-2-ol in dry dichloromethane (DCM) is added 1 equivalent of freshly distilled triethylamine (in dry DCM) under nitrogen over a period of 30 min at 0° C. After 1 h, the resulting solution is treated with 2.4 g of fluoroacryloyl chloride dissolved in 5 mL dry DCM over 30 min at 0° C. The resulting solution is stirred overnight at room temperature and hydrolyzed by the addition of 50 mL of distilled water. The aqueous phase is extracted with ethyl ether and the combined organic phase is dried over MgSO 4 . The crude product is purified by column chromatography.  
       EXAMPLE XXV  
     Synthesis of Compound (VI) Where R 2  is a Chlorine Atom  
       [0091]    To a solution of 1,1,1,3,3,3-hexafluoro-2-[4′-{2,2,2-trifluoro-1-[4-(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-cyclohexyl]-1-trifluoromethyl-ethyl}-1-cyclohexyl]-propan-2-ol in dry dichloromethane (DCM) is added 1 equivalent of freshly distilled triethylamine (in dry DCM) under nitrogen over a period of 30 min at 0° C. After 1 h, the resulting solution is treated with 2.4 g of chloroacryloyl chloride dissolved in 5 mL dry DCM over 30 min at 0° C. The resulting solution is stirred overnight at room temperature and hydrolyzed by the addition of 50 mL of distilled water. The aqueous phase is extracted with ethyl ether and the combined organic phase is dried over MgSO 4 . The crude product is purified by column chromatography.  
       EXAMPLE XXVI  
     Synthesis of Compound (XII)  
       [0092]    To a solution of 1,1,1,3,3,3-hexafluoro-2-[3-(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-cyclohexyl]-propan-2-ol in dry THF, is added n-butyllithium (1 equivalent) under nitrogen during 30 minutes followed by dropwise addition of bicyclo[2.2.1]hept-5-ene-2-carbonyl chloride (1 equivalent) dissolved in dry THF. The resulting solution is stirred overnight at room temperature and hydrolyzed by the addition of distilled water. The aqueous phase is extracted with ethyl ether, and the combined organic phase is dried over MgSO 4 . The crude product is purified by column chromatography.  
       EXAMPLE XXVII  
     Synthesis of Compound (XIII)  
       [0093]    To a solution of 1,1,1,3,3,3-hexafluoro-2-[6-(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-decahydro-naphthalen-2-yl]-propan-2-ol in dry THF, is added n-butyllithium (1 equivalent) under nitrogen during 30 minutes followed by dropwise addition of bicyclo[2.2.1]hept-5-ene-2-carbonyl chloride (1 equivalent) dissolved in dry THF. The resulting solution is stirred overnight at room temperature and hydrolyzed by the addition of distilled water. The aqueous phase is extracted with ethyl ether, and the combined organic phase is dried over MgSO 4 . The crude product is purified by column chromatography.  
       EXAMPLE XXVIII  
     Synthesis of Compound (XIV)  
       [0094]    To a solution of 1,1,1,3,3,3-hexafluoro-2-[6-(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-tetradecahydro-anthracen-2-yl]-propan-2-ol in dry THF, is added n-butyllithium (1 equivalent) under nitrogen during 30 minutes followed by dropwise addition of bicyclo[2.2.1]hept-5-ene-2-carbonyl chloride (1 equivalent) dissolved in dry THF. The resulting solution is stirred overnight at room temperature and hydrolyzed by the addition of distilled water. The aqueous phase is extracted with ethyl ether, and the combined organic phase is dried over MgSO 4 . The crude product is purified by column chromatography.  
       EXAMPLE XXIX  
     Synthesis of Compound (XVIII)  
       [0095]    To a solution of 1,1,1,3,3,3-hexafluoro-2-{4′-[(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-cyclohexyloxy]cyclohexyl}-propan-2-ol in dry THF, is added n-butyllithium (1 equivalent) under nitrogen during 30 minutes followed by dropwise addition of bicyclo[2.2.1]hept-5-ene-2-carbonyl chloride (1 equivalent) dissolved in dry THF. The resulting solution is stirred overnight at room temperature and hydrolyzed by the addition of distilled water. The aqueous phase is extracted with ethyl ether, and the combined organic phase is dried over MgSO 4 . The crude product is purified by column chromatography.  
       EXAMPLE XXX  
     Synthesis of Compound (XV)  
       [0096]    To a solution of 1,1,1,3,3,3-hexafluoro-2-[4′-(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-bicyclohexyl-4-yl]-propan-2-ol in dry THF, is added n-butyllithium (1 equivalent) under nitrogen during 30 minutes followed by dropwise addition of bicyclo[2.2.1]hept-5-ene-2-carbonyl chloride (1 equivalent) dissolved in dry THF. The resulting solution is stirred overnight at room temperature and hydrolyzed by the addition of distilled water. The aqueous phase is extracted with ethyl ether, and the combined organic phase is dried over MgSO 4 . The crude product is purified by column chromatography.  
       EXAMPLE XXXI  
     Synthesis of Compound (XVI)  
       [0097]    To a solution of 1,1,1,3,3,3-hexafluoro-2-[4′-{2,2,2-trifluoro-1-[4-(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-cyclohexyl]-1-trifluoromethyl-ethyl}-cyclohexyl]-propan-2-ol in dry THF, is added n-butyllithium (1 equivalent) under nitrogen during 30 minutes followed by dropwise addition of bicyclo[2.2.1]hept-5-ene-2-carbonyl chloride (1 equivalent) dissolved in dry THF. The resulting solution is stirred overnight at room temperature and hydrolyzed by the addition of distilled water. The aqueous phase is extracted with ethyl ether, and the combined organic phase is dried over MgSO 4 . The crude product is purified by column chromatography.  
       EXAMPLE XXXII  
     Synthesis of Compounds (Ia) and (XIa) Where R 1  Not Present and Hexafluoroisopropyl Attaches at Various Carbons  
       [0098]    Preparation of bis(2-hydroxyhexafluoroisopropyl)maphthalene:  
                         
 
         [0099]    Naphthalene (12 g. 93.7 mmol), aluminum chloride (2 g. 15 mmol), and 50 mL of carbon disulfide were charged to a 300 mL Parr reactor in a dry box. This was then connected to a metal vacuum line and the reactor cooled with a dry ice-acetone bath. The line and the head space of the reactor were evacuated. The bath was removed and the temperature brought up to room temperature. Hexafluoroacetone was condensed in 20 to 30 psi increments (total of 200 psi, 182 mmol). There was a very slow pressure drop and no temperature increase. Addition of hexafluoroacetone took three days. Unreacted hexafluoroacetone was purged into a 5M sodium hydroxide solution and the reaction mixture was added to 200 mL of water. The two phases were separated and the aqueous layer further extracted with chloroform. The combined organic layer was dried over magnesium sulfate, filtered and the solvent evaporated in vacuo. Analysis (GC/MS) showed clean reaction with several isomers present. The product was purified by column chromatography on silica gel with elution using hexane, followed by 1:5 ethyl acetate:hexane, and characterized by GC/MS and NMR. Results show that the sample contains two major and three minor isomers.  
         [0100]    Preparation of bis(2-hydroxyhexafluoroisopropyl)decalin:  
         [0101]    A short path distillation was performed on 22 g. of bis(2-hydroxyhexafluoroisopropyl)naphthalene at 102-105° C. and 0.04 torr to give 15 g of clear white very viscous oil.  
         [0102]    Into a one liter stainless steel Parr autoclave was placed 15 g. of the above naphthalene material, 12.1 g of 4% Rh on alumina (Engelhard) and 500 mL of isopropanol. After nitrogen and hydrogen purging, the reactor was put under 476 psig of hydrogen and heated to 100° C. and the hydrogen pressure adjusted to 800 psig. The reaction was allowed to proceed for 600 minutes. At that time GC/MS analysis revealed that a small amount of material was incompletely hydrogenated. The reaction was allowed to proceed an additional 800 minutes. A sample analyzed at this time revealed no additional hydrogenation had occurred. The reactor contents were cooled, filtered and concentrated in vacuo and then submitted to a short path distillation at 100-104° C. and 0.04 torr to give 13.3 g of a clear colorless liquid. The isomers of bis(2-hydroxyhexafluoroisopropyl)decalin were confirmed by GC/MS. The absence of any aromaticity was confirmed by  13 CNMR; however, approximately 4 mole percent of a material containing a quaternary olefin was observed.  
         [0103]    Preparation of (Ia) and (XIa):  
         [0104]    The isomers with or without separation from each other are reacted with acryloyl chloride or bicyclo[2.2.2]hept-5-ene-2-carbonyl chloride or 5-chlorobicyclo[2.2.1]hept-2-ene.  
       EXAMPLE XXXIII  
     Synthesis of Polymer (XVII)  
       [0105]    To a 25 mL Schlenk flask was added the monomer (III), 2,2′-azobisisobutyronitrile (1 mol % to monomer) and anhydrous tetrahydrofuran (30% solution in v/v). The reaction was degassed by the freeze-thaw method (3 times), sealed under nitrogen, and then immersed into an oil bath thermostated at 65° C. After 24 hours polymer was obtained by precipitating in methanol and drying in vacuum. The polymer obtained had the structure (XVII) where n=7. The absorbance at 157 nm was measured to be 2.4 μm −1 .  
         [0106]    Variations  
         [0107]    Many variations will be obvious to those skilled in the art. Therefore the invention is defined by the claims.