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¡¡ SOG Á¤¸®
SOG Spin on glass: Si-O network polymers in organic solvents, Silanol compound¿Í Solvent°¡ È¥ÇյǾî ÀÖ´Â ¾×ü ¿ë¾× 

[ Silanol compound : RnSi(OH)4n ] + Solvent

º¸°ü ³ÃÀå º¸°ü, »ç¿ë½Ã ²¨³» »ó¿Â¿¡¼­ »ç¿ë
Á¦Á¶ TEOS (tetraetoxysilane) À»  Hydrolysis (°¡¼ö ºÐÇØ:¹°À» ÷°¡ÇÏ¿© ºÐÇØ)  ¹æ¹ýÀ¸·Î Á¦Á¶

Si(OC2H5)4), water (H2O) , isopropanol ((CH5)2CH(OH)) and hydrochloric acid (HCl).

Because TEOS and water are immiscible, the reactions only begin when the solvent
isopropanol is added. The reactions took place at 82oC, the boiling temperature of
isopropanol. The reaction rate can be controlled by adding an acid as catalyst;
hydrochloric acid was used in this case.

even with excess water (r >> 2), the reaction does not go to completion.
Instead, a spectrum of intermediate species are generated. The intermediates, which
remain soluble in the alcohol-water medium, are silanols, ethoxylanols, and
polysiloxanes. Depending on this molar ratio, different kinds of product, e.g. bulk gel,
film, fiber, and power, could be obtained. Beside the r value, the catalyst type and
concentration, the solvent, temperature, and pressure also cause modifications in the
structure and properties of the polysilicate products.

The final product (silicate SOG) will be a transparent sol of organic solvents (ethanol,
acetone, isopropanol) containing Si-O network polymers. These above reactions will continue with time even at room temperature and may result in dense sol of larger network polymers. If this happens the SOG will not be able to be applied uniformly on a substrate because of its very high viscosity. In order to prevent these reactions the SOG should be stored at low temperature (3oC is sufficient). Even though, the shelf life of silicate SOG is limited to six months.

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Tetraethyl orthosilicate 99.999% trace metals basis      Synonym: Orthosilicic acid tetraethyl ester, TEOS, Tetraethoxysilane
  • Linear Formula: Si(OC2H5)4,  Molecular Weight: 208.33, CAS Number: 78-10-4

TEOS MSDS

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Æ®¸®¿¡Åå½Ã½Ç¶õ 11.27g, ¸ÞÆ¿ÀÌ¼ÒºÎÆ¿ÄÉÅæ 15.56g, Áú»ê/¹°(0.0006% ¼ö¿ë¾×) 1.2g ¹× ¹° 1.2gÀ» 50ml ¹ÝÀÀ±â¿¡ ³Ö°í 4½Ã°£ µ¿¾È À¯Áö

Ư¡ SOG ÀÇ Æòźȭ Ư¼º, ±â°èÀû ¹°¼º ¹× µµÆ÷¼º µîÀº, Æ÷ÇÔµÈ À¯±â ¿ë¸ÅÀÇ Á¾·ù¿Í

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ºÐÀÚ·®ÀÌ Áö³ªÄ¡°Ô ³·Àº °æ¿ì:  »ó´ëÀûÀ¸·Î ¹Ðµµ°¡ ³·Àº Àý¿¬¸·ÀÌ Çü¼ºµÇ¾î, Àý¿¬¸·ÀÇ ±â°èÀû ¹°¼ºÀÌ ÀúÇϵǴ µ¿½Ã¿¡, ½ºÇÉ ÄÚÆÃ ÈÄÀÇ º£ÀÌÅ·½Ã¿¡ ±Õ¿­¿¡ ´ëÇÑ ÀúÇ×¼ºÀÌ ³·¾ÆÁø´Ù.


ºÐÀÚ·®ÀÌ Áö³ªÄ¡°Ô Å©°Ô µÇ´Â °æ¿ì: Á¥À½ Ư¼ºÀÌ ¶³¾îÁ®¼­, »ó  ±â Àý¿¬¸· Çü¼º¿ë Á¶¼º¹°ÀÌ Á¾È¾ºñ°¡ Å©°Ô Çü¼ºµÈ »ó±â ¹è¼± ¶Ç´Â Àü±Ø »çÀÌ¿¡ Àß ½º¸çµéÁö ¸øÇϱ⠶§¹®¿¡, Àý¿¬¸· ³»¿¡ ´Ù¼öÀÇ °øµ¿À» Çü¼º.

ºÐÀÚ·® ºÐÆ÷°¡ ³Ð¾îÁú¼ö·Ï, Àý¿¬¸· ³»ÀÇ ÀÔÀÚ¿Í ÀÔÀÚ »çÀ̰¡ Ä¡¹ÐÇÏ°Ô Ã¤¿öÁüÀ¸·Î¼­, Æòźȭ°¡°ø µî¿¡ ÀÇÇÑ ¿µÇâ ÀÚü°¡ ÃÖ¼ÒÈ­µÇ¾î Àý¿¬¸·ÀÇ Æòźȭ Ư¼ºÀÌ Çâ»óµÇ¸ç, Àý¿¬¸·ÀÌ »ê ¶Ç´Â ¿°±â µî¿¡ ´ëÇØ¼­µµ °­ÇÑ ÀúÇ×¼ºÀ» °¡Áö°Ô µÇ°í, ¹Ðµµ°¡ Å« Àý¿¬¸·ÀÌ Çü¼ºµÇ¾î Àý¿¬¸·ÀÇ ±â°èÀû ¹°¼ºÀÌ Çâ»óµÈ´Ù

°øÁ¤ Coating Á¡µµ¿Í ½ºÇÉ ¼Óµµ·Î µÎ²² Á¶Àý
¡¡ Bake For the purpose of out-gassing, the drying temperature should be approximately 250 oC.
¡¡ Cure To go from sticky gel to a hard gel usually takes about 30 minutes at temperatures less than 600 oC, Water and solvent evaporate through interconnected pores which remain open at the surface.

The micro porosity in silica is not removed entirely until 1000 oC, but it may already behave as an oxidation barrier or passivation coating at 600 oC. This ability of the micro-porous film to behave in many ways like the bulk oxide is an attractive property of the sol-gel approach to coating.

¡¡ ¡¡
Silicate based SOG

Silanol (Si-OH) compound¿¡ CH3 ±âÀÇ Á¸Àç À¯¹«¿¡ µû¶ó Silicate¿Í Siloxane °è·Î ³ª´©¾î Áö´Âµ¥ CH3 ±â °¡ ¾ø´Â °æ¿ì´Â silicate °èÀÌ´Ù.

The silicate SOG is formed from a condensation reaction of Si(OH)4 by losing water. When the film is fully cured, the film should form a strong Si-O network and contain no -OH but it has fairly significant shrinkage.

Organosilicon SOG (Siloxane SOG)

Siloxane type SOG´Â Si ¿øÀÚ¿¡ Silanol group°ú Methyl group(-CH3)ÀÌ °áÇÕ. Siloxane°è´Â Silicate°è¿¡ ºñÇØ Á¡µµ°¡ Ä¿¼­ µµÆ÷ ÈÄ¿¡ Æòźµµ°¡ ¿ì¼öÇϰí Methyl groupÀ» ÇÔÀ¯Çϰí Àֱ⠶§¹®¿¡ bakingÇÏ´Â °úÁ¤¿¡¼­ ¸·ÀÇ ¼öÃàÀ» ¸·À» ¼ö ÀÖÀ¸¸ç ÀÌ·Î ÀÎÇÑ stressµµ ÀÛ¾Æ ¸·ÀÇ CrackÀÇ ÀúÇ×¼ºÀÌ Å©´Ù´Â ÀåÁ¡,

contains –CH3 or –C2H5 types of organic dopants. the organic group modifies the Si-O network which lowers the film stress to 200 MPa, typically. The viscosity and molecular weight are slightly higher than that of the silicate SOG. The film is thicker than that of the silicate SOG using the
same spin speed and its planarity is better

It has been observed that some of the siloxane SOG films pick up atmospheric water and this may become a reliability issue or cause extensive processing constraints.

It can be seen from the FTIR spectra before and after 400 oC baking that Si-OR and Si-R (R stand for organic groups) peaks disappear and Si-OH peaks show up.

The - OH content not only reduces the device performance (due to high dielectric constant) but also creates reliability issues.

Increasing the organic content will further reduce the film stress and improve the crack resistance and planarity.

 SPIN-ON GLASS MATERIALS AND APPLICATIONS IN ADVANCED IC TECHNOLOGIES

Àý¿¬Àç·á  
 Siloxane °è°¡ Film³» CarbonÀÌ O2¿Í ¹ÝÀÀÇÏ´Â ÀÌÀ¯·Î Silicate °è¿¡ ºñÇØ ¼öÃàÀÌ Å©´Ù. ¶ÇÇÑ 420¡É/30ºÐ Anneal ÈÄ¿¡ H2O¿Í CH3¿Í °°Àº À¯±â¹°ÀÌ ¹ß°ßµÇÁö ¾Ê¾Æ ÃÖ¼ÒÇÑ 420¡É Á¤µµÀÇ CuringÀÌ ÇÊ¿äÇÏ´Ù.            
                         Siloxane °è                Silicate °è    
    N2 ºÐÀ§±â          10.7%                        20.5%    
    O2 ºÐÀ§±â          14.4%                        19.9%  
¿ë¾×°øÁ¤À¸·Î °¸ÇÊ °¡´É °øÁ¤. ¾Æ·¡±×¸²°ú °°ÀÌ ±íÀº ÄÁÅÃÀ» ä¿ì°í Æòźȭ ±â´É.  Á¼°í ±íÀº ÄÁÅÿ¡ PECVD µîÀ¸·Î ÁõÂø ÇÏ¸é ¿À¸¥ÂÊ ±×¸²°ú °°ÀÌ void°¡ »ý±æ ¼ö ÀÖÀ½

    

¡¡¡¡TOK»ç Type-7 SOG´Â Siloxane °è¿­ÀÇ ¹°Áú·Î PE oxide¿Í adhesion ÀÌ ÁÁÁö ¾ÊÀº °ÍÀ¸·Î º¸°íµÇ¾î ÀÖÀ¸¸ç ÀÌÀÇ °³¼±À» À§ÇØ O2 plasma ó¸® ȤÀº UV Cure󸮸¦ ÇÏ¸é °³¼±µÇ´Â °ÍÀ¸·Î ¾Ë·ÁÁ® ÀÖÀ½. ¾Æ·¡ »çÁøÀº SOG À§ PETEOS oxide adhesion ºÒ·® SEM»çÁø

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¡¤ÀåÁ¡ : Liquid sourceÀÇ Coating ÇüÅ·ΠÆòÅÁÈ­ È¿°ú°¡ ¶Ù¾î³ª°í, ºñ¿ëÀÌ Àú·Å.
¡¤´ÜÁ¡ : Curing½Ã H2OÀÇ OutgassingÀ¸·Î ÀÎÇÑ Crack ¹ß»ý ¹× Film³»¿¡ Á¸ÀçÇÏ´Â
Carbon¿¡ ÀÇÇÑ Polymer Çü¼º ¹× Via ÀúÇ× »ó½Â.

¡¡           OH               OH             
             |                  |             
     OH - Si - OH + O = X - OR + Solvent                       SOLUTION
             |                  |             
          OH               OH             
¡¡          O        OH              OH             
           |          |                 |             
     O - Si - O - Si - O + O = X - OR                             POROUS
           |          |                 |             
        OH       O               OH                           (After Spinning ¡­ 150¡É)
¡¡           O         O          O         O             
           |          |          ¡«         |             
     O - Si -   O - Si - O - X - O - Si - O -                     GLASSY
           |          |           |         |             
           O         O          O         O                        (Heated at 250¡É ¡­ 350¡É) 
                      |            |         |             
                   - Si -       OR     - Si -             
                      |                      |             
¡¡           O         O          O         O             
           |          |          ¡«         |             
     O - Si - O - Si - O - X - O - Si - O -                      INORGANIC
           |          |           |          |             
           O         O          O         O                               (Heated at 350¡É ¡­ 600¡É) 
           |          |           |          |             
     O - Si - O - Si - O - X - O - Si - O -             
           |          |           |          |             
           O         O          O         O
           |          |           |          |
     O - Si - O - X  - O - Si -
           |          ¡«
           O          O
¡¡ ¡¡
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Àç·á ³×ÆÐ½º SOG Cospeen-1225G

³×ÆÐ½º ƯÇã

Cospeen-1225G is methyl-siloxane-based organic spin-on-glass coating solution

• Planarization > 90% at 1 ¥ìm feature
• Coating thickness 2300 ¡Ê - 4000 ¡Ê per coat
• Bake temperature / time 80oC / 2 min - 230oC / 4 min
• Cure temperature / time 450oC / 30 min in N2
Âü°í¹®Çå SPIN-ON GLASS MATERIALS AND APPLICATIONS IN ADVANCED IC TECHNOLOGIES