TW201034082A - Fabricating method of crystalline film and fabricating apparatus of the same - Google Patents
Fabricating method of crystalline film and fabricating apparatus of the same Download PDFInfo
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- 238000000034 method Methods 0.000 title abstract description 27
- 239000013078 crystal Substances 0.000 claims abstract description 66
- 239000000758 substrate Substances 0.000 claims abstract description 52
- 238000002844 melting Methods 0.000 claims abstract description 23
- 230000008018 melting Effects 0.000 claims abstract description 23
- 238000002425 crystallisation Methods 0.000 claims description 53
- 230000008025 crystallization Effects 0.000 claims description 48
- 238000004519 manufacturing process Methods 0.000 claims description 24
- 239000013081 microcrystal Substances 0.000 claims description 13
- 230000003287 optical effect Effects 0.000 claims description 10
- 238000005286 illumination Methods 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 claims description 3
- 241000282320 Panthera leo Species 0.000 claims 1
- 239000004990 Smectic liquid crystal Substances 0.000 claims 1
- 239000003638 chemical reducing agent Substances 0.000 claims 1
- 235000018553 tannin Nutrition 0.000 claims 1
- 229920001864 tannin Polymers 0.000 claims 1
- 239000001648 tannin Substances 0.000 claims 1
- 239000010408 film Substances 0.000 description 108
- 239000010410 layer Substances 0.000 description 19
- 238000001069 Raman spectroscopy Methods 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 13
- 239000007790 solid phase Substances 0.000 description 12
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 11
- 229910052707 ruthenium Inorganic materials 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 229910052732 germanium Inorganic materials 0.000 description 9
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 9
- 239000011521 glass Substances 0.000 description 8
- 238000005224 laser annealing Methods 0.000 description 8
- 238000005401 electroluminescence Methods 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
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- 229910052715 tantalum Inorganic materials 0.000 description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 4
- 238000002679 ablation Methods 0.000 description 3
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- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000003841 Raman measurement Methods 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02524—Group 14 semiconducting materials
- H01L21/02532—Silicon, silicon germanium, germanium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/02—Positioning or observing the workpiece, e.g. with respect to the point of impact; Aligning, aiming or focusing the laser beam
- B23K26/06—Shaping the laser beam, e.g. by masks or multi-focusing
- B23K26/073—Shaping the laser spot
- B23K26/0732—Shaping the laser spot into a rectangular shape
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02367—Substrates
- H01L21/0237—Materials
- H01L21/02422—Non-crystalline insulating materials, e.g. glass, polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02656—Special treatments
- H01L21/02664—Aftertreatments
- H01L21/02667—Crystallisation or recrystallisation of non-monocrystalline semiconductor materials, e.g. regrowth
- H01L21/02675—Crystallisation or recrystallisation of non-monocrystalline semiconductor materials, e.g. regrowth using laser beams
- H01L21/02686—Pulsed laser beam
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier
- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being other than a semiconductor body, e.g. an insulating body
- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
- H01L27/1259—Multistep manufacturing methods
- H01L27/127—Multistep manufacturing methods with a particular formation, treatment or patterning of the active layer specially adapted to the circuit arrangement
- H01L27/1274—Multistep manufacturing methods with a particular formation, treatment or patterning of the active layer specially adapted to the circuit arrangement using crystallisation of amorphous semiconductor or recrystallisation of crystalline semiconductor
- H01L27/1285—Multistep manufacturing methods with a particular formation, treatment or patterning of the active layer specially adapted to the circuit arrangement using crystallisation of amorphous semiconductor or recrystallisation of crystalline semiconductor using control of the annealing or irradiation parameters, e.g. using different scanning direction or intensity for different transistors
Abstract
Description
201034082201034082
• · · X 六、發明說明： 【發明所屬之技術領域】 本發明是有關於一種結晶質膜的製造方法以及製造裝 置，該製造方法是對非晶質膜照射脈衝雷射光（pulse laser) ’使該非晶質膜進行微細結晶化而製作結晶質膜。 【先前技術】 為了製造液晶顯示裝置等薄型顯示器平板顯示器（flat panel display )中所使用的薄膜電晶體（Thin Film Transistor ’ TFT)的結晶矽（cryStailized siiic〇n)，通常使 用如下兩種方法：對設置於基板上層的非晶矽（am〇fph〇us silicon)膜照射脈衝雷射光而使其熔融、再結晶化的方法 (雷射退火法（laser annealing method));以及將上層具有 非晶矽膜的上述基板於加熱爐中進行加熱，使上述矽膜不 熔融而以固體狀態進行結晶成長的固相成長法（s〇UdBACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and a device for producing a crystalline film which is irradiated with a pulsed laser of an amorphous film. The amorphous film is finely crystallized to form a crystalline film. [Prior Art] In order to manufacture a crystal film (CryStailized siiic) of a thin film transistor (TFT) used in a flat panel display such as a liquid crystal display device, the following two methods are generally used: a method of irradiating and recrystallizing a pulsed laser light on an amorphous germanium (μ〇fph〇us silicon) film provided on an upper layer of a substrate (laser annealing method); and having an upper layer amorphous A solid phase growth method in which the above-mentioned substrate of the ruthenium film is heated in a heating furnace to cause the ruthenium film to be melted and crystallized in a solid state (s〇Ud)
Phase Crystallization，SPC )。 另外，本發明者等人確認到如下情況並將其提出：藉 由在/將基板溫度保持為加熱狀態的狀態下照射脈衝雷射 光，從而藉由固相成長來獲得微細的多結晶膜（參昭 文獻1)。 ’ ' 先前技術文獻 專利文獻 專利文獻1 :曰本專利特開2008-147487號公報 一近年來，於製造大型電視（television，TV)用有機發 光一極體（〇rgamc Light Emitti叫 面板或 201034082 液晶顯示器（Liquid Crystal Display，LCD )面板時，謀求 廉價地製造均勻且大面積的微細多結晶矽膜的方法。 ❹Phase Crystallization, SPC). In addition, the inventors of the present invention have confirmed that it is possible to obtain a fine polycrystalline film by solid phase growth by irradiating pulsed laser light while maintaining/maintaining the substrate temperature in a heated state. Zhao literature 1). ' ' 。 。 。 。 。 。 。 。 。 。 。 。 近年来 近年来 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 近年来 近年来 近年来 近年来 近年来 近年来 近年来 gam gam gam gam gam gam gam gam gam gam gam gam gam gam gam gam gam gam gam gam gam gam In the case of a liquid crystal display (LCD) panel, a method of producing a uniform and large-area fine polycrystalline ruthenium film at low cost is desired.
另外，最近’代替液晶顯示器，作為下一代顯示器而 被看好的有機電激發光（Electro-Luminescence，EL)顯示 器中’藉由有機EL自身發光而提高螢幕（screen)的亮度。 有機EL的發光材料並非是如LCD的電壓驅動，而是電流 驅動，因此對TFT的要求不同。利用非晶矽的TFT難以 抑制經年變化’會產生臨界電壓（threshold voltage，Vth ) 的大幅度漂移（drift)’使元件的壽命受限。另一方面，多 晶矽（polysilicon)由於是穩定材料故壽命長。然而，利用 多晶梦的TFT中，TFT的特性不均(fluctuati〇n)大。該TFT 特性的不均是由於結晶粒徑的不均、或結晶質矽的晶粒的 界面（BB界）存在於TFT的通道（Channei)形成區域而更 容易產生。TFT的特性不駐要㈣被存在於通道間的結 ^粒徑與晶界的數量所影響。此外，若結晶_大，則通 2電子遷移率（electron m〇bmty)變大。有機el顯示器 途的TFT右電場電子遷料高，則反而必需延長Further, recently, in the case of an organic electroluminescence (EL) display which is favored as a next-generation display in place of a liquid crystal display, the brightness of the screen is increased by the organic EL itself. The organic EL luminescent material is not driven by a voltage such as an LCD, but is driven by a current, and thus the requirements for the TFT are different. It is difficult to suppress the change of the annual voltage by the amorphous germanium TFT, which causes a large drift of the threshold voltage (Vth), which limits the life of the element. On the other hand, polysilicon has a long life because it is a stable material. However, in a TFT using polycrystalline dreams, the characteristics of the TFT are not uniform (fluctuati). The unevenness of the TFT characteristics is more likely to occur due to the unevenness of the crystal grain size or the interface (BB boundary) of the crystal grains of the crystal grains existing in the channel forming region of the TFT (Channei). The characteristics of the TFT are not resident (4) and are affected by the size of the junction between the channels and the number of grain boundaries. Further, when the crystal _ is large, the electron mobility (electron m〇bmty) becomes large. The organic EL display on the way to the right electric field of the TFT is high, but it must be extended.
TFT 度’導致臟(紅、綠、藍)各自的1晝素的大 於釺：叙:FT的通道長度，無法獲得高解析度。因此，對 高。。曰曰、乂的不均小且微細的結㈣的要絲度越發提 2 ’先前的結晶方法難以解決上述問題。 是伟^日因在於，作為先前的結晶方法之一的雷射退火法 疋使非晶㈣時㈣而再結晶化的製程（ΡΓΓ)，通ί 201034082 所形成的結晶粒徑大，結晶粒徑的不均亦大。因此，如上 所述’電場電子遷料U個TFT的通道區域内的結晶 粒徑數產生不均的情況、或無規的形狀、相鄰結晶的結晶 配向性的差異會對TFT的特性不均造成較大影響。尤其於 雷射重合部容易出現結晶性的差異，該結晶性的差異 TFT的特料均造成較场響。另外，亦存在由於表面的 污染物（contamination)(雜質）而使結晶產生缺陷的 題。 —另外，利用固相成長法（SPC法）獲得的結晶，其粒 挫小且TFT不均少，是解決上述問題的最有效的結晶方 法。然而，結晶化時間長，難以作為量產用途來採用。於 可進行固相成長法（SPC)的熱處理步驟中，是使用可對 多片基板同時進行處理的批式（batch type)熱處理裝置。 由於對大量基板同時進行加熱，故升溫及降溫需要長時 間，並且基板内的溫度容易變得不均勻。另外，固相成長 法若於比玻璃基板的應變點溫度更高的溫度下長時間加 熱，則會引起玻璃基板自身的收縮、膨脹，對玻璃造成損 傷。由於SPC的結晶化溫度高於玻璃轉移點，故於少量的 /JHL度分布中產生玻璃基板的撓曲或收縮分布。其結果，即 使可進行結晶化，亦於曝光步驟等的製程中產生障礙，使 元件的製作變得困難。處理溫度越高，越要求溫度均勻性。 通常結晶化速度依存於加熱溫度，於6〇〇〇c下需要1〇小時 〜15小時的處理時間，於650。〇下需要2小時〜3小時的 處理時間，且於700X：下需要數1〇分鐘的處理時間。為了 201034082The degree of TFT' causes dirty (red, green, and blue) to be larger than 1 昼: :: FT channel length, high resolution cannot be obtained. Therefore, it is high. . The unevenness of the 曰曰 and 乂 are small and the fineness of the fine knot (4) is more advanced. 2 The previous crystallization method is difficult to solve the above problem. It is because of the laser anneal method which is one of the previous crystallization methods, and the process of recrystallization (a) in the case of amorphous (four) (4), and the crystal grain size formed by ί 201034082 is large, and the crystal grain size is large. The unevenness is also large. Therefore, as described above, the difference in the number of crystal grain sizes in the channel region of the U-TFTs for electric field electron relocation, or the random shape, and the difference in crystal orientation of adjacent crystals may cause uneven characteristics of the TFT. Causes a greater impact. In particular, the difference in crystallinity is likely to occur in the laser overlap portion, and the difference in crystallinity causes a relatively loud noise. In addition, there is also a problem that crystals are defective due to contamination (impurities) of the surface. - In addition, the crystal obtained by the solid phase growth method (SPC method) has a small particle size and a small TFT unevenness, and is the most effective crystallization method for solving the above problems. However, the crystallization time is long and it is difficult to use it as a mass production application. In the heat treatment step in which solid phase growth (SPC) can be performed, a batch type heat treatment apparatus which can simultaneously process a plurality of substrates is used. Since a large number of substrates are simultaneously heated, it takes a long time to raise and lower the temperature, and the temperature in the substrate tends to become uneven. Further, when the solid phase growth method is heated for a long period of time at a temperature higher than the strain point temperature of the glass substrate, the glass substrate itself shrinks and swells, causing damage to the glass. Since the crystallization temperature of the SPC is higher than the glass transition point, a deflection or shrinkage distribution of the glass substrate occurs in a small amount of /JHL degree distribution. As a result, even if crystallization is possible, an obstacle occurs in the process such as the exposure step, which makes it difficult to fabricate the device. The higher the processing temperature, the more uniform the temperature is required. Generally, the crystallization rate depends on the heating temperature, and a treatment time of 1 Torr to 15 hours is required at 650 ° C at 650. It takes 2 hours to 3 hours to process, and it takes 1 minute to process at 700X:. For 201034082
L 在不對玻璃基板造成損傷的情況下進行處理，需要長時間 的處理時間，故該方法難以作為量產用途而採用。 【發明内容】 本發明是以上述情況為背景研究而成，目的在於提供 一種結晶質膜的製造方法，該製造方法可不對基板造成損 傷，而由非晶質膜來效率良好地製作結晶粒徑的不均少的 微細結晶質膜。 ，即，本發明的結晶質膜的製造方法中，第一本發明的 特徵在於.以1次〜10次的發數（shot number)對位於基 板的上層的非晶質膜照射由340 nm〜358 nm的波長所構 成、且具有130 mJ/cm2〜24〇 mJ/cm2的能量密度的脈衝雷 射光’將上料晶質膜加熱至不超過結晶熔點的溫度而使 本發明的結晶質膜的製造裝置的特徵在於包括：脈衝 雷射光源其輸出波長為34〇 nm〜358咖的脈衝雷射光； 光學系統’其將上述脈衝雷射光導引至非晶質膜上而進行L is treated without damage to the glass substrate, and requires a long processing time. Therefore, this method is difficult to use as a mass production application. SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the invention is to provide a method for producing a crystalline film which can efficiently produce a crystal grain size from an amorphous film without causing damage to a substrate. A fine crystalline film with less unevenness. In the method for producing a crystalline film of the present invention, the first aspect of the invention is characterized in that the amorphous film located on the upper layer of the substrate is irradiated by 340 nm to a shot number of one to ten times. Pulsed laser light having a wavelength of 358 nm and having an energy density of 130 mJ/cm 2 to 24 〇 mJ/cm 2 'heats the charged crystal film to a temperature not exceeding the melting point of the crystal to make the crystalline film of the present invention The manufacturing apparatus is characterized by comprising: a pulsed laser light source having pulsed laser light having an output wavelength of 34 〇 nm to 358 Å; and an optical system for guiding the pulsed laser light onto the amorphous film
^上^^雜她小其對自上述脈衝雷射光源輸 雷射光的衰減率進行調整以使上述雷射光 上;以及掃描裝置，其使上述雷射光對上述非晶質= =二使上述脈衝雷射光在上述非晶質膜上 10發的範圍内進行重疊照射。 态二’藉由將紫外線波長區域的脈衝雷射光以 適度㈣量錢與適度的發數來照射至非晶質膜上，進行 201034082 t— 2=2非晶質膜經加熱至不超過結晶熔點的溫度， 從而了以與先前的熔融、再結晶 的不均小的均勺斜如钍曰,，， j打々泛术獲得粒授 例如尺寸為小於等於5〇腿且 。於先前方式的熔融結晶法中，結晶粒 ’另外，該熔融結晶法或细加熱爐 ，曰C (固相成長法）t，晶粒的不均變大，無法獲得微 、、、田、、，口 晶0 另外，依據本發明’由於僅加熱至*超過結晶溶點的 >皿度，故經結晶化的膜自身不會再進行相變，例如由於僅 ，非晶石夕變化為結晶梦，故於脈衝雷射光的重合部位亦獲 得同樣的結晶性，均勻性提高。此外，藉由本發明條件下 的脈衝雷射光的騎，可將非晶f膜加熱纽先前的固相 成長法高的溫度。 另外，藉由並非連續振盪而是採用脈衝雷射光，則基 底的基板不易達到受損傷的溫度。此外，本發明中不需要 進行基板的加熱，但本發明並不排除進行基板加熱的方 法。但是，本發明較理想的是不進行基板的加熱而照射上 述脈衝雷射光。 此外’設置於基板上的非晶質膜若氫含量多，則於以 如熔融結晶法的高能量進行照射時，si_H的分子鍵容易斷 裂’容易剝蝕（ablation)，故有脫氫的情況，但本發明中， 矽是以固相的狀態變化，不易產生剝蝕，故可對不脫氫的 非晶質膜進行處理。 其次’以下對本發明所規定的條件進行說明。 201034082 波長區域：340nm〜358 nm .b上述波長區域對於非晶質膜、尤其是非晶矽膜而言， 疋吸收良好的波長區域，故可_該波長區域的脈衝雷射 光對非晶質膜進行直接加熱。因此，無需在非晶質膜的上 層間接地設置雷射吸收層。另外，由於雷射光在非晶質膜 上被充分吸收，故可防止基板被雷射光加熱，基板的撓曲 及變形得到抑制，可避免基板的損傷。 ❹此外，若雷射光的波長對於非晶質膜、尤其是非晶矽 膜而言，為雖有吸收但亦透射的波長，則由於自下層侧的 多重反射，而導致對於非晶質膜的照射部分的光吸收率大 幅依存於非晶質膜下層的厚度的偏差（不均）。若雷射光的 波長為上述波長區域，則雷射光在非晶質膜、尤其是矽膜 的表層可完全吸收，因此可不太考慮下層的膜厚不均而獲 得多結晶膜。另外，可幾乎忽視非晶質膜的透射，因此亦 可應用於在金屬上形成有非晶質膜者。 即，若將用於結晶化的雷射光的波長區域設為可見光 ❹ 區域，則50 nm厚左右的矽雖吸收光，但亦存在透射的光， 因此自矽下層（SiCVSiN層等緩衝層（buffer layer))的 多重反射影響，若不使矽下層的緩衝層的厚度均勻，則存 在矽的光吸收率亦變化的問題。於矽的上層設置Si〇2等覆 蓋層（capping layer)的方式亦同樣地存在問題。 另外’若將脈衝雷射光的波長區域設為紅外線區域， 則50 nm厚左右的碎基本不吸收光，故通常於石夕的上層部 設置光吸收層。但是，若使用本方式，則存在塗佈光吸收 201034082 層的步驟、及於脈衝雷射照射後去除該光吸收層的步驟自 然增加的問題。 自上述各觀點考慮，本案發明中將脈衝雷射光的波長 區域設定為紫外線區域的340 nm〜358 nm。 能量密度：130 mJ/cm2〜240 mJ/cm2 藉由對非晶質膜照射能量密度適度（非晶質膜上）的 脈衝雷射光，則非晶質膜以固相的狀態進行結晶化，或者 經加熱至超過非晶熔點且不超過結晶熔點的溫度而結晶 化，從而可製作微結晶。若能量密度低，則非晶質膜的溫 度並不充分提岗，結晶化不充分進行，或結晶化變得困難。 另一方面，若能量密度高，則導致產生熔融結晶，或者產 生剝蝕。因此’將脈衝雷射光的能量密度限定為13〇mJ/cm2 〜240 mJ/cm2。 發數：1次〜1〇次 對非晶質膜照射脈衝雷射光時，藉由適當地設定對同 二區域照射的發數，則即使於所照射的光束面積内存在能 量不均，亦可藉由多次照射而使結晶化的溫度變得均勻， 結果可製作均勻的微結晶。 若發數多，則非晶質膜經加熱至超過結晶熔點的溫 度存在產生炼融或者剝姓的情況。另外，隨著發數的增 大，處理時間變長，效率差。 結晶率：60%〜95% f理想的是於上述波長、能量密度、發數的條件内， 將、”Q μ化時的結晶率設定為6〇%〜95%。若結晶率小於 201034082 =% ’則用作薄膜電晶體等時變得難以獲得充分的特性。 右對非晶質膜提供的能量少，則無法使結晶率大於等於 60%。另外，若結晶率超過95%，則結晶的粗大化得以進 展’變得難以獲得微細且均勻的結晶。若超過 照射脈衝祕光，則純率料變得超過95^ ‘，來 此外’具體而言，結晶率可根據藉由拉曼分光（R_n spectroseopy )峨得的結晶波峰的面積以及非結晶波岭的 面積的比率（結晶Si波蜂的面積/(非結晶Si波峰的面積 擊 +結晶Si波峰的面積））來決定。 曰此外，脈衝雷射光的脈衝寬度（半值寬度）較理想的 是設為5 ns〜_ ns。若脈衝寬度小，則峰值功率密度增 大有經加熱至超過熔點的溫度而熔融或者剝钱(她触) 的情況。若脈衝寬度大，則峰值功率密度減小，有無法加 熱至使其進行固相結晶化的溫度的情況。 並且，脈衝雷射光的脈衝頻率較理想的是6 kHz〜1〇 kHz 〇 ❹ 藉由脈衝雷射光的脈衝頻率提高至某程度（大於等於 6 kHz) ’則每發之間的時間間隔變小，脈衝雷射光照射的 熱於非晶質膜上得以保持，因此有效地作用於結晶化。另 一方面，若脈衝頻率變得過高，則變得容易產生熔融、剝 韻。 另外，上述脈衝雷射光的短軸寬度較理想的是設為小 於等於1.0 mm。 藉由將脈衝雷射光在短軸寬度方向上相對地掃描，可 11 201034082 十非日日質膜進行部分地照射 ， 的結晶化處理。但，若短軸 ： 好地結晶化，必以大游變㈣A’麟了效率良 藉由將K、+、/掃私速度’從而導致裝置成本增大。 上述非晶_、=衝雷射辆非㈣助對輯描，可使 射先描可使脈衝雷 行。較理想的是以50聰⑸〜1_ mm/sec的速度進 況。另外，若播生溶融或者剝姓的情 加献至使歧’則峰值功率密度減小，有無法 *、、、使其進仃固相結晶化的溫度的情況。 衝雷=的使用輸出紫外線區域的脈 光，可利用= 輸出所需波長區域的脈衝雷射 ❹ 微結晶。為了=rrrnce)性良好的雷射光源來製作 量調整部來適當:調2==:衝雷射光可利用能 能量靜t _源的功率進行調整而獲得預定的 減率進^整=自固體雷射光源輸出的脈衝雷射光的衰 用掃整能量密度。該脈衝雷射光可藉由利 域以晶質膜相對地掃描，而於非晶質膜的大區 以對相二;=獲得微細且均句的結晶。藉由該掃描， 來設定脈衝的;成為^的方式 J馮丰、脈衝雷射光的短軸寬度、掃描速度。 12 201034082 掃描裝置可為使導引脈衝雷射光的光學系統移動而使 脈衝雷射光移動的裝置，另外，亦可為使配置有非晶質膜 的基台移動的裝置。 [發明效果] 如以上所說明，依據本發明，可對位於基板的上層的 非晶質膜，以1次〜10次的發數來照射由340nm〜358 nm ❹ ❹ 的波長所構成、且具有130 mj/cm2〜24〇 mJ/cm2的能量密 度的脈衝雷射光，將上述非晶質膜加熱至不超過結晶熔點 的溫度而使其結晶化，因此可製作平均粒徑小的結晶質 膜，該結晶質膜可於TFT的通道區域存在多個晶粒且具有 特別優異的均勻性，從而可解決上述問題。最近，隨著配 線^變小，TFT的通道形成區域的尺寸（通道長度、通 道寬度）亦變小，因此謀求可於基板整個區域均勻地製作 平均粒徑小的穩定的結晶質膜。尤其謀求使鄰接區域的 τ T特f生之差成為最小的結晶化技術利用本發明可確實 地實現上述迫切期望。同時亦可去除 =用的減少化，可進行運行率高的處理，因此可提高生產 Μ孩Ϊ外’、依據本發明’由於是不超過基板（玻璃等）的 或者即使超過轉移點亦可於低溫下進行處理的製 僅使非晶質膜以雷射加熱至高溫而使其結晶化。 果。同短時間内生成小於等於5Gnm的微結晶的效 〇、重。部亦具有同樣的生成小於等於50腿的微結 13 201034082 ——Λ.. 晶的效果（對大面積的結晶化有效）。 並且’本發明具有將基板的變位（撓曲、變形、内部 應力）抑制為最小限度的效果。同時本發明具有藉由對基 板多少進行加熱，而去除非晶質膜内所存在的雜質及附著 於表面的污染物的效果。 為讓本發明之上述和其他目的、特徵和優點能更明顯 易懂，下文特舉較佳實施例，並配合所附圖式，作詳細說 明如下。 【實施方式】 ❹ 以下’基於圖1來對本發明的一實施形態進行說明。 於該實施形態的結晶質膜的製造方法中，是以平板顯 示器TFT元件中所使用的基板8為對象，於該基板8上形 成非晶矽薄膜8a作為非晶質膜。非晶矽薄膜8a是利用常 法而形成於基板8的上層，省略脫氫處理。 但是’本發明中成為對象的基板以及形成於該基板上 的非晶質臈的類別並不限定於上述類別。 圖1表示本發明一實施形態的結晶質膜的製造方法中 ❿ 所使用的紫外線固體雷射退火處理裝置1，該紫外線固體 退火處理裝置1相當於本發明的結晶質膜的製造裝置。 紫外線固體雷射退火處理裝置1中，輸出具有340 run 〜358 nm的波長且脈衝頻率為6kHz〜1〇kHz、脈衝寬度 為5 ns〜1〇〇 ns的脈衝雷射光的紫外線固體雷射振盪器2 設置於除振台6上’且於該紫外線固體雷射振盪器2上包 括生成脈衝信號的控制電路2a。 14 201034082^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ The laser light is superimposed and irradiated in a range of 10 on the amorphous film. State 2' is irradiated onto the amorphous film by pulsed laser light in the ultraviolet wavelength region with a moderate (four) amount and a moderate number of shots, and the 201034082 t-2 = 2 amorphous film is heated to not exceed the crystalline melting point. The temperature is such that, in comparison with the previous melting and recrystallization unevenness, the snoring is obtained, for example, the size is 5 or less. In the melt crystallization method of the prior art, the crystal grains 'in addition, the melt crystallization method or the fine heating furnace, 曰C (solid phase growth method) t, the grain unevenness becomes large, and it is impossible to obtain micro, and, and, Further, according to the present invention, the film which is crystallized does not undergo phase change again because it is heated to only * beyond the crystal melting point, for example, since only amorphous austenite changes to crystal Dream, so the same crystallinity is obtained in the overlapping portion of the pulsed laser light, and the uniformity is improved. Further, by riding the pulsed laser light under the conditions of the present invention, the amorphous f film can be heated to a high temperature of the previous solid phase growth method. Further, by using pulsed laser light instead of continuous oscillation, the substrate of the substrate is less likely to reach the damaged temperature. Further, in the present invention, heating of the substrate is not required, but the present invention does not exclude a method of heating the substrate. However, in the present invention, it is preferable that the pulsed laser light is irradiated without heating the substrate. In addition, when the amorphous film provided on the substrate has a large hydrogen content, when it is irradiated with high energy such as melt crystallization, the molecular bond of si_H is easily broken, and it is easily ablated, so that dehydrogenation is caused. However, in the present invention, ruthenium is changed in a solid phase state, and ablation is less likely to occur, so that an amorphous film which is not dehydrogenated can be treated. Next, the conditions specified in the present invention will be described below. 201034082 Wavelength region: 340nm to 358 nm .b The above-mentioned wavelength region absorbs a good wavelength region for an amorphous film, especially an amorphous germanium film, so that the pulsed laser light of the wavelength region can be used for the amorphous film. Direct heating. Therefore, it is not necessary to indirectly provide the laser absorbing layer in the upper layer of the amorphous film. Further, since the laser light is sufficiently absorbed on the amorphous film, the substrate can be prevented from being heated by the laser light, and the deflection and deformation of the substrate can be suppressed, and the damage of the substrate can be avoided. In addition, if the wavelength of the laser light is an absorption wavelength but an transmission wavelength for the amorphous film, especially the amorphous germanium film, the amorphous film is irradiated due to multiple reflection from the lower layer side. The partial light absorption rate largely depends on the variation (unevenness) in the thickness of the underlayer of the amorphous film. If the wavelength of the laser light is in the above-mentioned wavelength region, the laser light can be completely absorbed in the surface layer of the amorphous film, particularly the ruthenium film, so that a much more crystalline film can be obtained without considering the uneven film thickness of the lower layer. Further, since the transmission of the amorphous film can be almost ignored, it can also be applied to those in which an amorphous film is formed on a metal. In other words, when the wavelength region of the laser light used for crystallization is a visible light 区域 region, 矽 of about 50 nm thick absorbs light, but there is also transmitted light. Therefore, the buffer layer (buffer layer such as SiCVSiN layer) The effect of multiple reflection of layer)), if the thickness of the buffer layer of the underlayer is not uniform, there is a problem that the light absorptivity of the crucible also changes. A method of providing a capping layer such as Si〇2 in the upper layer of the crucible is similarly problematic. Further, when the wavelength region of the pulsed laser light is the infrared region, the chip having a thickness of about 50 nm does not substantially absorb light. Therefore, a light absorbing layer is usually provided in the upper portion of the stone slab. However, according to this embodiment, there is a problem that the step of applying the light absorption 201034082 layer and the step of removing the light absorbing layer after the pulsed laser irradiation naturally increase. From the above viewpoints, in the invention of the present invention, the wavelength region of the pulsed laser light is set to 340 nm to 358 nm in the ultraviolet region. Energy density: 130 mJ/cm 2 to 240 mJ/cm 2 By irradiating the amorphous film with pulsed laser light having an appropriate energy density (on the amorphous film), the amorphous film is crystallized in a solid phase state, or Crystallization is carried out by heating to a temperature exceeding the amorphous melting point and not exceeding the melting point of the crystal, whereby microcrystallization can be produced. When the energy density is low, the temperature of the amorphous film is not sufficiently lifted, crystallization is insufficient, or crystallization becomes difficult. On the other hand, if the energy density is high, melt crystallization or ablation occurs. Therefore, the energy density of the pulsed laser light is limited to 13 〇 mJ/cm 2 to 240 mJ/cm 2 . Number of shots: When the pulsed laser light is irradiated to the amorphous film once or twice, if the number of shots irradiated to the same area is appropriately set, even if there is uneven energy in the area of the irradiated light beam, The temperature of crystallization is made uniform by multiple irradiations, and as a result, uniform microcrystals can be produced. If the number of shots is large, the amorphous film may be heated or peeled off at a temperature exceeding the melting point of the crystal. In addition, as the number of shots increases, the processing time becomes longer and the efficiency is poor. Crystallinity: 60% to 95% f is preferably within the conditions of the above wavelength, energy density, and number of shots, and the crystallinity at the time of "Q μ is set to 6〇% to 95%. If the crystallinity is less than 201034082 = When %' is used as a thin film transistor or the like, it becomes difficult to obtain sufficient characteristics. When the energy supplied to the amorphous film is small, the crystallinity cannot be made 60% or more. Further, if the crystallinity exceeds 95%, the crystal is crystallized. The coarsening progresses. It becomes difficult to obtain fine and uniform crystals. If the illuminating pulse is exceeded, the pure rate becomes more than 95^', and in addition, the crystallization rate can be based on Raman spectroscopy. (R_n spectroseopy ) The ratio of the area of the crystal peak and the area of the amorphous crystal (the area of the crystal Si bee/(the area of the amorphous Si peak + the area of the crystal Si peak)) is determined. The pulse width (half-value width) of the pulsed laser light is preferably set to 5 ns to _ ns. If the pulse width is small, the peak power density is increased by melting to a temperature exceeding the melting point to melt or strip money (she touches Case if the pulse width When the voltage is large, the peak power density is reduced, and there is a case where the temperature at which the solid phase crystallization cannot be heated can be heated. Further, the pulse frequency of the pulsed laser light is preferably 6 kHz to 1 〇 kHz by pulsed laser light. The pulse frequency is increased to a certain extent (6 kHz or more) 'The time interval between each shot becomes smaller, and the heat of the pulsed laser light is maintained on the amorphous film, thus effectively acting on the crystallization. On the other hand, if the pulse frequency becomes too high, melting and flaking are likely to occur. Further, the short-axis width of the pulsed laser light is preferably 1.0 mm or less. By pulsed laser light on the short axis Relatively scanning in the width direction, 11 201034082 Ten non-Japanese solar film is partially irradiated and crystallized. However, if the short axis: good crystallization, it must be a large change (4) A' Lin has good efficiency. The speed of K, +, / sweeping will result in an increase in the cost of the device. The above-mentioned amorphous _, = rushing lasers are not (four) assisted pairs, so that the first shot can be used to make the pulse ray. Ideally, 50 Cong (5) ~ 1_ mm / sec speed In addition, if the broadcast is melted or the stripping of the surname is added to the difference, the peak power density is reduced, and there is a case where the temperature of the solid phase cannot be crystallized. By using the pulse light in the output ultraviolet region, it is possible to use the pulse laser ❹ microcrystals of the desired wavelength region to be output. For the laser source with good rrnce, the amount adjustment unit is made appropriate: tune 2==: rushing laser light The energy of the energy static t _ source can be adjusted to obtain a predetermined deceleration rate = the aging energy density of the pulsed laser light output from the solid laser light source. The pulsed laser light can be crystallized by the domain The plasma membrane is scanned relatively, and in the large area of the amorphous film, the phase is aligned; = fine and uniform crystallization is obtained. By this scanning, the pulse is set; the mode of becoming J is Feng Feng, the short axis width of the pulsed laser light, and the scanning speed. 12 201034082 The scanning device may be a device that moves the optical system that guides the pulsed laser light to move the pulsed laser light, or may be a device that moves the base on which the amorphous film is disposed. [Effect of the Invention] As described above, according to the present invention, the amorphous film located in the upper layer of the substrate can be irradiated with a wavelength of 340 nm to 358 nm ❹ 1 from one to ten times, and has an Pulsed laser light having an energy density of 130 mj/cm 2 to 24 〇 mJ/cm 2 , which crystallizes the amorphous film to a temperature not exceeding the melting point of the crystal, thereby producing a crystalline film having a small average particle diameter. The crystalline film can have a plurality of crystal grains in the channel region of the TFT and has particularly excellent uniformity, so that the above problem can be solved. Recently, as the wiring line becomes smaller, the size (channel length, channel width) of the channel formation region of the TFT is also reduced. Therefore, it is possible to uniformly form a stable crystalline film having a small average particle diameter in the entire region of the substrate. In particular, the crystallization technique for minimizing the difference between the τ and T of the adjacent regions can surely achieve the above-mentioned urgent needs by the present invention. At the same time, it is also possible to remove the reduction in use, and it is possible to carry out a treatment with a high operation rate, so that the production can be improved, and according to the present invention, it is not necessary to exceed the substrate (glass or the like) or even if it exceeds the transfer point. The treatment is carried out at a low temperature, and only the amorphous film is heated to a high temperature by laser to be crystallized. fruit. The effect and the weight of the microcrystals of 5 Gnm or less are generated in a short time. The Ministry also has the same micro-junction that generates less than or equal to 50 legs. 13 201034082 - Λ.. Effect of crystal (effective for large-area crystallization). Further, the present invention has an effect of suppressing displacement (deflection, deformation, internal stress) of the substrate to a minimum. At the same time, the present invention has the effect of removing impurities present in the amorphous film and contaminants adhering to the surface by heating the substrate somewhat. The above and other objects, features and advantages of the present invention will become more <RTIgt; [Embodiment] ❹ Hereinafter, an embodiment of the present invention will be described based on Fig. 1 . In the method for producing a crystalline film of the embodiment, the substrate 8 used in the flat panel display TFT device is used, and the amorphous germanium film 8a is formed on the substrate 8 as an amorphous film. The amorphous tantalum film 8a is formed on the upper layer of the substrate 8 by a usual method, and the dehydrogenation treatment is omitted. However, the type of the substrate to be targeted in the present invention and the amorphous germanium formed on the substrate are not limited to the above categories. Fig. 1 shows an ultraviolet solid-state laser annealing treatment apparatus 1 used in a method for producing a crystalline film according to an embodiment of the present invention. The ultraviolet solid annealing treatment apparatus 1 corresponds to a production apparatus of a crystalline film of the present invention. In the ultraviolet solid-state laser annealing treatment apparatus 1, an ultraviolet solid-state laser oscillator having a pulsed laser beam having a wavelength of 340 run to 358 nm and a pulse frequency of 6 kHz to 1 〇 kHz and a pulse width of 5 ns to 1 〇〇 ns is outputted. 2 is disposed on the vibration removing table 6' and includes a control circuit 2a for generating a pulse signal on the ultraviolet solid-state laser oscillator 2. 14 201034082
L ^外線固體雷射㈣器2的輸出側配置有衰減器 2弱器）3,且於衰減器3的輸出側經由結合器4而連接 5。光纖5的傳送目的地上連接有光學系統7，該光 …7包括聚光透鏡（condensing lens) 7〇a、7〇b與配 置於該聚光透鏡70a、70b間的光束均句器（be、am J7rize0 71a、71b等。於光學純7的出射方向上設 、置基板8的基板載置台9。光學纽7是以將脈衝The output side of the L^ external solid-state laser (four) 2 is provided with an attenuator 2 weaker) 3, and is connected to the output side of the attenuator 3 via a combiner 4. An optical system 7 is connected to the transmission destination of the optical fiber 5, and the light 7 includes a condensing lens 7〇a, 7〇b and a beam collimator disposed between the collecting lenses 70a and 70b (be, Am J7rize0 71a, 71b, etc. The substrate mounting table 9 on which the substrate 8 is placed in the emission direction of the optical pure 7 is used.
❹ 2光整形為短軸寬度小於等於1G職的長方形或者線 光束狀的方式來設定。 上述基板載置台9可沿著該基板载置台9的面方向 方向）移動，且該基板載置台包括使該基板載置台9 b者上述面方向高速移動的掃描裝置 接者，對使用上述紫外線固體雷射退火處理裝置1的 非晶矽薄膜的結晶方法進行說明。 首先，於基板載置台9上載置上層形成有非晶矽薄膜 8a的基板8。於該實施形態中，不對該基板8進行加熱器 (heater)等的加熱。 控制電路2a中，以輸出預先設定的脈衝頻率（6 kHz 〜10 kHz)、且脈衝寬度為5 ns〜1〇〇 ns的脈衝雷射光的方 式生成脈衝信號，然後根據該脈衝信號自紫外線固體雷射 振盈器2中輸出波長為340 nm〜358 nm的脈衝雷射光。 自紫外線固體雷射振盪器2輸出的脈衝雷射光到達衰 減器3，通過該衰減器3而以預定的衰減率衰減。該衰減 率疋以在加工面上脈衝雷射光達到本發明規定的能量密度 15 201034082 ^---- X--- 的”。衰減器3可使衰減率可變。 f密度經娜騎衝雷射光是由光纖5傳送而導入 70、7m!統、7中。光學系統7中，如上所述利用聚光透鏡 勒站官#光束均勻器7U、71b等，將脈衝雷射光整形為 ^又小於等於10麵的長方形或者線光束狀對基板 m m：r/em2〜24() m;/em2的能量密度進行昭 射。 ，❹ 2 Light shaping is set in such a way that the short axis width is less than or equal to the 1G position of the rectangle or the line beam. The substrate mounting table 9 is movable along the surface direction of the substrate mounting table 9, and the substrate mounting table includes a scanner device that moves the substrate mounting table 9b at a high speed in the surface direction, and uses the ultraviolet solid. A method of crystallizing the amorphous tantalum film of the laser annealing treatment apparatus 1 will be described. First, the substrate 8 on which the amorphous germanium film 8a is formed is placed on the substrate stage 9. In this embodiment, the substrate 8 is not heated by a heater or the like. In the control circuit 2a, a pulse signal is generated by outputting a pulsed laser light having a preset pulse frequency (6 kHz to 10 kHz) and a pulse width of 5 ns to 1 〇〇ns, and then based on the pulse signal from the ultraviolet solid ray The output oscillator 2 outputs pulsed laser light having a wavelength of 340 nm to 358 nm. The pulsed laser light output from the ultraviolet solid-state laser oscillator 2 reaches the attenuator 3, and is attenuated by the attenuator 3 at a predetermined attenuation rate. The attenuation rate 脉冲 is to pulse the laser light on the processing surface to reach the energy density of the present invention 15 201034082 ^---- X---". The attenuator 3 can make the attenuation rate variable. The light is transmitted from the optical fiber 5 and introduced into the 70, 7m system, 7. In the optical system 7, the pulse laser light is shaped into ^ and smaller than the above using the condensing lens to stand the #beam uniformizer 7U, 71b and the like as described above. A rectangular or line beam shape equal to 10 faces is used to illuminate the energy density of the substrate mm:r/em2~24() m; /em2.
壯里"f述基板載置台9是沿著非晶⑦薄膜8a面，利用掃描 裝置10而於上述線光束的短軸寬度方向上移動其結果， 於該非晶料膜83面陳廣區域，將±述 相對地掃描-面照射。另外，此時藉由狀利用射H 的移動速度’而使脈衝雷㈣的掃描速度為5G _^〜 =00 mm/sec，且於非晶矽薄膜％的同一區域以丨次〜⑺ 次的發數來重疊（overlap)照射脈衝雷射光。該發數是基 於上述脈衝_率、脈衝寬度、脈衝雷射光驗軸寬度ΐ 脈衝雷射光的掃描速度而決定。 ❹ 藉由上述脈衝雷射光的照射，僅基板8上的非晶矽薄 膜8a經加熱而於短時間内多結晶化。此時，非晶矽薄膜 h的加熱溫度成為不超過結晶熔點的溫度（例如超過1〇〇〇 C〜1400 C左右）。此外，加熱溫度可設為不超過非晶熔點 溫度的溫度、或者超過非晶熔點溫度但不超過結晶熔點的 溫度。 藉由上述照射而獲得的結晶質薄膜，其結晶粒徑為小 於等於50 nm，且無先前的固相結晶成長法中所看到的突 16 201034082 起，具有均勻且微細的優質結晶性。例如，可適宜列舉平 均晶粒小於等於20 nm、且標準偏差小於等於丨〇 nm的結 晶質薄膜。晶粒可利用原子力顯微鏡（at〇mic f〇rce microscope，AFM)來測定。另外，所獲得的結晶可基於 拉曼分光的結晶波峰的面積與非結晶波峰的面積之比來算 出結晶率，該結晶率較理想的是〜95%。 上述結晶質薄膜可適宜用於有機EL顯示器。但，本 發明的使用用途並不限定於上述有機EL顯示器，可作為 其他的液晶顯示器或電子材料來使用。 此外’上述實施形態中是藉由使基板載置台移動而使 脈衝雷射光相對地掃描，但亦可為藉由使導引脈衝雷射光 的光學系統高速移動而使脈衝雷射光相對地掃描。 實例1 接著，一面與比較例進行比較一面對本發明的實例進 行說明。 使用上述實施形態的紫外線固體雷射退火處理裝置 Φ 卜對利用常法而形成於玻璃製基板的表面的非晶矽薄膜進 行照射脈衝雷射光的實驗。 該實驗中，將脈衝雷射光的波長設為355 nm的紫外 線區域光，將脈衝頻率設為8 kHz，且將脈衝寬度設為 nsec。能量密度是利用衰減器3來調整為對象能量密度。 脈衝雷射光是利用光學系統而整形為在加工面上成為 圓形，改變加工面的能量密度、光束尺寸、發數，對基板 上的非晶矽膜照射脈衝雷射光。非晶矽經加熱而變化為結 17 201034082 晶矽。根據圖2中所示的掃描式電子顯微鏡（Scanning Electron Microscope，SEM )照片來對該經照射的薄膜進行 評價。另外，將各條件以及評價結果示於表1中。 關於將脈衝雷射光的能量密度設為70 mj/cm2而經照 射的薄膜，若將發數設為8000次，則如照片i所示，可製 作10 rnn〜20 nm的微結晶。但是，發數多而需要長時間 的處理，因此在工業上並不適合。The substrate mounting table 9 is moved along the surface of the amorphous 7 film 8a by the scanning device 10 in the direction of the minor axis width of the line beam, and the amorphous film 83 is covered. The relative scanning-surface illumination is performed. In addition, at this time, the scanning speed of the pulse Ray (4) is 5 G _ ^ 〜 = 00 mm / sec by the moving speed ' of the shot H, and is 丨 ~ (7) times in the same region of the amorphous 矽 film % The number of shots overlaps the illuminating pulsed laser light. The number of rounds is determined based on the pulse rate, the pulse width, the pulse width of the pulsed laser light, and the scanning speed of the pulsed laser light.照射 By the irradiation of the above-described pulsed laser light, only the amorphous tantalum film 8a on the substrate 8 is heated to be polycrystallized in a short time. At this time, the heating temperature of the amorphous tantalum film h is a temperature not exceeding the crystal melting point (for example, more than about 1 〇〇〇 C to 1400 C). Further, the heating temperature may be set to a temperature not exceeding the amorphous melting point temperature or a temperature exceeding the amorphous melting point temperature but not exceeding the crystalline melting point. The crystalline film obtained by the above irradiation has a crystal grain size of 50 nm or less, and has no uniform crystal fineness as compared with the protrusion 16 201034082 seen in the previous solid phase crystal growth method. For example, a crystalline film having an average crystal grain size of 20 nm or less and a standard deviation of 丨〇 nm or less can be suitably cited. The crystal grains can be measured by an atomic force microscope (AFM). Further, the obtained crystal can be calculated based on the ratio of the area of the crystal peak of Raman splitting to the area of the amorphous peak, and the crystal ratio is preferably 〜95%. The above crystalline film can be suitably used for an organic EL display. However, the use of the present invention is not limited to the above-described organic EL display, and can be used as another liquid crystal display or an electronic material. Further, in the above embodiment, the pulsed laser light is relatively scanned by moving the substrate stage, but the pulsed laser light may be relatively scanned by moving the optical system for guiding the pulsed laser light at a high speed. Example 1 Next, an example of the present invention will be described while comparing with a comparative example. The ultraviolet solid-state laser annealing treatment apparatus of the above-described embodiment was used to illuminate an amorphous ruthenium film formed on the surface of a glass substrate by a conventional method. In this experiment, the wavelength of the pulsed laser light was set to 355 nm ultraviolet region light, the pulse frequency was set to 8 kHz, and the pulse width was set to nsec. The energy density is adjusted to the target energy density by the attenuator 3. The pulsed laser light is shaped into a circular shape on the machined surface by an optical system, and the energy density, the beam size, and the number of hairs of the machined surface are changed, and the pulsed laser light is irradiated onto the amorphous ruthenium film on the substrate. The amorphous germanium is heated to change into a junction 17 201034082. The irradiated film was evaluated according to the Scanning Electron Microscope (SEM) photograph shown in Fig. 2. In addition, each condition and evaluation result are shown in Table 1. When the film having an energy density of pulsed laser light of 70 mj/cm 2 is irradiated, if the number of shots is 8,000, as shown in the photograph i, microcrystals of 10 rnn to 20 nm can be produced. However, the number of shots is large and requires long-term processing, so it is not suitable for industrial use.
另外’關於將能量密度設為70 mJ/cm2且發數為800 次的薄膜，非晶薄膜未經結晶化。其原因在於， 過低^使增加發數，亦達不雜晶I、此量在度 接著’當將脈衝雷射光的能量密度設為14〇mj/cm2、 160 mJ/cm2、180 mJ/cm2、200 mJ/cm2 時，如照 2〜6 所 示，獲得均勻的微細結晶。 然後’當將脈衝雷射光的能量密度設為25〇 mJ/cm2 時、、1如照#7所示，上轉晶賴經加熱至超過結晶溶點 的溫度崎融’因此成為熔融結晶，未獲得微細結晶。Further, regarding the film having an energy density of 70 mJ/cm 2 and a number of occurrences of 800 times, the amorphous film was not crystallized. The reason is that if the number is too low, the number of shots is increased, and the amount of crystals is not increased. The amount is then 'when the energy density of the pulsed laser light is set to 14〇mj/cm2, 160 mJ/cm2, and 180 mJ/cm2. At 200 mJ/cm2, as shown in 2 to 6, uniform fine crystals were obtained. Then, when the energy density of the pulsed laser light is set to 25 〇mJ/cm2, as shown in #7, the upper crystal crystallization is heated to a temperature exceeding the melting point of the crystallization point, so that it becomes molten crystal, and thus Fine crystallization is obtained.
進而，當將脈衝雷射光的能量密度設為26〇 mJ/cm2 時，如照片8所示產生剝蝕。 如以上所不，藉由將脈衝雷射光的能量密度、脈衝寬 發數設定為適當的顧，可首次進行均勻且微細的結 晶化。 =述照片所明示，由本發明法所獲得的多結晶石夕薄 ^^:晶粒徑的不均少，於面整體經均質地多結晶化， 件優f的多結晶⑦薄膜。另外，同時可4認重合部 18 201034082 亦生成同樣的均勻微結晶。已判明，晶粒小於等於50 nm， 較小，且亦未產生突起，均勻地獲得結晶質矽膜，因此可 提供TFT特性的不均少的矽膜。 [表1]Further, when the energy density of the pulsed laser light was set to 26 〇 mJ/cm 2 , the ablation was generated as shown in the photograph 8. As described above, by setting the energy density and the pulse width of the pulsed laser light to an appropriate level, uniform and fine crystallization can be performed for the first time. In the above-mentioned photograph, the polycrystalline skeletal thin film obtained by the method of the present invention has a small unevenness in crystal grain size, and is multi-crystalline 7 film which is homogeneously polycrystalline in the entire surface. In addition, at the same time, the same uniform microcrystals can be generated by the coincidence portion 18 201034082. It has been found that crystal grains of 50 nm or less are small, and no protrusions are formed, and a crystalline ruthenium film is uniformly obtained, so that a ruthenium film having less unevenness in TFT characteristics can be provided. [Table 1]
19 201034082 20 狀態 SEM照片 發數 光束尺寸 能量密度 (mJ/cm2 ) 均勻微細結 晶 照片1 8000 1 -Θ- 未結晶化 1 800 一 圓 -Θ- 均勻微細結 晶 |照片2 1 4^ 國 -Θ- 140 均勻微細結 晶 |照片3 j ·—* ρ 1—* 隱 -Θ- 1—4 S 均勻微細結 晶 |照片4 1 K> P 3 3 -Θ- t—* s 均勻微細結 晶 |照片5 1 P 3 3 -θ- 180 均勻微細結 晶 |照片6 1 1—* ρ 令 200 熔融結晶 |照片7 1 1 0.1 mm φ 250 _____i 剝蝕 |照片8 1 1—* ρ 1 -θ- 260 33912pif Θ e 201034082 接著，一面與比較例進行比較一面對本發明的其他實 例進行說明。 ' 使用上述實施形態的紫外線固體雷射退火處理裝置 1 ’對利用常法而形成於玻璃製基板的表面的非晶石夕薄膜進 行照射脈衝雷射光的實驗。該實驗中，將脈衝雷射光的波 長設為355 nm的紫外線區域光，將脈衝頻率設為6kHz〜 8 kHz ’且將脈衝寬度設為go ns (nsec)。脈衝能量密度是 利用衰減器3來調整為對象能量密度。發數是利用平台速 度進行調整而成為對象發數。將各供試材料的能量密度、 發數不於表2中。另外，將以下所測定的結晶率同樣地示 於表2中。 脈衝雷射光是利用光學系統而整形為在加工面上成為 長方开>，然後對基板上的非晶石夕進行。非晶石夕經加熱而變 化為結晶石夕。根據圖3、圖4中所示的SEM照片與圖' 5所 例示的拉曼分光測定來評價該經照射的薄膜。結晶率是基 於拉曼分光測定結果，利用結晶Si波峰的面積/(非結晶Si ❹ 波峰的面積+結晶Si波峰的_)的計算式⑴而算出。 於以下的實例以及比較例中，具體而言，是對5〇 nm 厚的薄膜’將波長為514.5 nm、功率為2碰的々離子 雷射光聚光為1 mm φ而照射，進行拉曼分光測定。圖5的 拉曼測定結果中可知’於52〇 cnfl附近存在結晶si的尖銳 波峰’且基本不存在480 cm-i附近的非晶&波岭。 進而基於測定結果，根據使用最小平方法的高斯擬合 (Gaussian fitting) ’分離為兩個波峰波形，然後利用上述 201034082 计异式（1)由各個波峰波形來算出結晶率。 圖5所不的例子為下述實例N〇J的資料，上述算出的 結果為’結晶率約為88%。 (實例2) 關於將脈衝雷射光的能量密度設為 130 mJ/cm2、且將 脈衝頻率設為6 kHz而照射有該脈衝雷射光的薄膜若將 發數設為6次，則如照片1G所示，可製作1() nm〜2〇她 直從的微結晶。根據拉曼分光測定對結晶率進行評價結19 201034082 20 State SEM photo generation beam size Energy density (mJ/cm2) Uniform fine crystal photo 1 8000 1 -Θ- Uncrystallized 1 800 One circle-Θ- Uniform fine crystal|Photo 2 1 4^ Country-Θ- 140 Uniform fine crystallization|Photo 3 j ·—* ρ 1—* Hidden-Θ-1–4 S Uniform fine crystal|Photo 4 1 K> P 3 3 -Θ- t—* s Uniform fine crystal|Photo 5 1 P 3 3 -θ- 180 Uniform Fine Crystallization|Photo 6 1 1—* ρ Let 200 Melt Crystallization|Photo 7 1 1 0.1 mm φ 250 _____i Erosion|Photo 8 1 1—* ρ 1 -θ- 260 33912pif Θ e 201034082 Next, One embodiment of the present invention will be described in comparison with a comparative example. Using the ultraviolet solid-state laser annealing treatment apparatus 1' of the above-described embodiment, an experiment was conducted to irradiate a pulsed laser beam on an amorphous slab film formed on the surface of a glass substrate by a conventional method. In this experiment, the wavelength of the pulsed laser light was set to 355 nm ultraviolet region light, the pulse frequency was set to 6 kHz to 8 kHz', and the pulse width was set to go ns (nsec). The pulse energy density is adjusted to the target energy density by the attenuator 3. The number of shots is adjusted by the platform speed and becomes the number of targets. The energy density and the number of hairs of each test material were not shown in Table 2. Further, the crystallization ratios measured below are shown in Table 2 in the same manner. The pulsed laser light is shaped into a rectangular opening on the processing surface by an optical system, and then is performed on the amorphous stone on the substrate. The amorphous stone is heated to change into a crystalline stone. The irradiated film was evaluated based on the SEM photographs shown in Figs. 3 and 4 and the Raman spectroscopic measurement illustrated in Fig. 5 . The crystallization ratio is calculated based on the Raman spectrometry result, and is calculated by the calculation formula (1) of the area of the crystal Si peak/(the area of the amorphous Si ❹ peak + the _ of the crystal Si peak). In the following examples and comparative examples, specifically, for a 5 〇 nm thick film, a krypton-ion laser light having a wavelength of 514.5 nm and a power of 2 collisions is condensed to 1 mm φ to perform Raman spectroscopy. Determination. In the Raman measurement results of Fig. 5, it is known that there is a sharp peak ' of crystal si in the vicinity of 52 〇 cnfl and there is substantially no amorphous & pulver near 480 cm-i. Further, based on the measurement results, two peak waveforms were separated according to a Gaussian fitting using the least square method, and then the crystallinity was calculated from the respective peak waveforms using the above-described 201034082 calculation equation (1). The example shown in Fig. 5 is the data of the following example N〇J, and the above calculated result is that the 'crystallinity ratio is about 88%. (Example 2) The film having the pulsed laser light having an energy density of 130 mJ/cm 2 and having a pulse frequency of 6 kHz and irradiated with the pulsed laser light is set to six times, as shown in the photograph 1G. Show, can make 1 () nm ~ 2 〇 her straight from the micro-crystal. Evaluation of crystallization rate according to Raman spectrometry
果為85°/❶。另外，即使將脈衝頻率設為8 kHz，亦獲得 樣的結果。 (實例3) 關於將脈衝雷射光的能量密度設為 140 mJ/cm2、且將: =衝頻率設為6他而照射有該脈衝雷射光的薄膜若將 發數設為6次，則如照片U所示，可製作1〇胍〜2〇她 的微結晶。根據拉曼分麵定騎晶率進行㈣，結果 88%。另外’即使將脈衝頻率設為skHz，亦獲得同樣的結 果。 、。The result is 85 ° / ❶. In addition, even if the pulse frequency is set to 8 kHz, the same result is obtained. (Example 3) The photo-density of the pulsed laser light is set to 140 mJ/cm2, and the film having the pulsed laser light is set to 6 and the pulsed laser light is set to 6 times. As shown by U, it is possible to make 1〇胍~2〇 her microcrystals. According to the Raman facet, the crystal riding rate is determined (4), and the result is 88%. In addition, even if the pulse frequency is set to skHz, the same result is obtained. ,.
(實例4) 關於將脈衝雷射光的能量密度設為 =衝頻較為6 kHz而照射有該脈衝雷射光的薄膜針 發數設為6次，則如照片12所示，可製作1〇唧〜2〇加 ，微結晶。根據拉曼分光測定對結晶率進行評價，結果為 〇°/〇。另外’即使將脈衝頻率設為8_，亦獲得同樣的舍 果0 、、 22 201034082 (實例5) 關於將脈衝雷射光的能量密度設為16〇 mJ/cm2、且將 脈衝頻率設為6 kHz而照射有該脈衝雷射光的薄膜，若將 發數設為6次，則如照片13所示，可製作20 nm〜30 nm 的微結晶。根據拉曼分光測定對結晶率進行評價，結果為 90%。另外’即使將脈衝頻率設為8kHz，亦獲得同樣的結 果。 、、° (實例6) 關於將脈衝雷射光的能量密度設為180 mJ/cm2、且將 脈衝頻率設為6 kHz而照射有該脈衝雷射光的薄膜，若將 發數設為6次’則如照片14所示，可製作20 nm〜30 nm 的微結晶。根據拉曼分光測定對結晶率進行評價，結果為 95%。另外，即使將脈衝頻率設為8kHz，亦獲得同樣的結 果。 ° (實例7) 關於將脈衝雷射光的能量密度設為200 mJ/cm2、且將 脈衝頻率設為6 kHz而照射有該脈衝雷射光的薄膜，若將 發數設為6次’則如照片15所示，可製作40 nm〜5〇 nm 的微結晶。根據拉曼分光測定對結晶率進行評價，結果為 95%。另外’即使將脈衝頻率設為8kHz，亦獲得同樣的結 果。 " (比較例1) 關於將脈衝雷射光的能量密度設為250 mJ/cm2、且將 脈衝頻率設為6 kHz而照射有該脈衝雷射光的薄膜，若將 23 201034082 Λ ^L/ΛΧ 發數設為6次，則如照片16所示，經加熱至超過熔點的溫 度而成為熔融結晶，未獲得均勻的結晶。根據拉曼分光測 定對結晶率進行評價，結果為97%。另外，即使將發數減 少至1次，亦獲得同樣的結果。 (比較例2) 關於將脈衝雷射光的能量密度設為26〇mJ/cm2、且將 脈衝頻率設為6 kHz而照射有該脈衝雷射光的薄膜，若將 發數设為6次’則如照片17所示產生剝姓。 (比較例3) © 關於將脈衝雷射光的能量密度設為12〇mj/cm2、且將 脈衝頻率設為8 kHz而照射有該脈衝雷射光的薄膜，若將 發數設為8次，則雖結晶化，但若進行gecc〇姓刻（gecc〇 etching)，則如照片18所示，結晶的有些部位經蝕刻。根 據拉曼分光測定對結晶率進行評價，結果為54%。 (實例8) 關於將脈衝雷射光的能量密度設為160 mJ/cm2、且將 脈衝頻率設為8 kHz而照射有該脈衝雷射光的薄膜，若將 ❾ 發數設為2次’則如照片19所示，可製作10 nm〜2〇 nm 的微結晶。根據拉曼分光測定對結晶率進行評價，結果為 75%。 (實例9) 關於將脈衝雷射光的能量密度設為180 mj/cm2、且將 脈衝頻率設為8 kHz而照射有該脈衝雷射光的薄膜，若將 發數设為2次’則如照片20所示’可製作1〇 nm〜20 nm 24 201034082 的微結晶。根據拉曼分光測定對結晶率進行評價，結果 78%。 、、’馬 (比較例4) 使用與上述實驗不同的波長為308 nm、脈衝寬度為 20 nsec的XeCl準分子雷射來進行同樣的實驗。關於^脈 衝雷射光的能量密度設為180 mJ/cm2、且將脈衝頻率設為 300 Hz而照射有該脈衝雷射光的薄膜，以發數8次使其結 ^ 晶化後，若為了進行SEM觀察而進行Secco蝕刻，則^ = 化部全部被蝕刻。根據拉曼分光測定對結晶率進行評價， 結果為54%。一般認為其原因在於，由於波長短而僅使表 層面結晶化。 (比較例5) 使用與上述實驗不同的波長為308 nm、脈衝寬度為 20 nsec的Xeci準分子雷射進行同樣的實驗。關於將脈衝 雷射光的能量密度設為200mJ/cm2、且將脈衝頻率設為3〇〇 Hz而照射有該脈衝雷射光的薄膜，若將發數設為8次則 鲁 如照片21所示’經加熱至超過結晶熔點的溫度而成為熔融 結晶，未獲得均勻的結晶。根據拉曼分光測定對結晶率進 行評價，結果為97%。 [表2] 25 201034082 26 狀態 晶粒大小 (nm) I結晶率（％) | SEM照片 發數（shot) 能量密度 (mJ/cm2) 脈衝頻率 |波長/脈衝寬度 供試材料 No. 1 0s ^ > 照片18 〇〇 1—» 8 kHz |355 nm/80 ns Ui |比較例 微細結晶 化 10 〜20 00 |照片10 | 6 kHz 355 nm/80 ns K3 實例 微細結晶 化 10 〜20 00 00 |照片11 | 〇\ OJ 微細結晶 化 10 〜20 名 I照片12 ! 〇\ 私 微細結晶 化 20 〜30 |照片13 1 〇\ S 微細結晶 化 10 〜20 ΰί |照片19 I K) t—* s 8 kHz 00 微細結晶 化 10 〜20 |照片20 | KJ g VO 微細結晶 化 20 〜30 \〇 Lh |照片14 j 〇\ 1—k tx 6 kHz ON 微細結晶 化 40 〜50 \〇 「照片15 1 〇\ to o -J 熔融結晶 大於等於 100 厂照片16 1 〇\ NJ 6 kHz 355 nm/80 ns »—» 比較例 剝蝕 1 |照片17| Os K) g K) Sm gl 據 1 〇〇 g 300 Hz 308 nm/20 ns 私 熔融結晶 1 VO |照片21 1 〇〇 o KJi 339.12pif 201034082 7此:=Γ工平均粒徑為15她，標準驗為 7 =比較例i中’平均結晶粒徑為72咖，標準偏差口 為 42 nm 〇(Example 4) When the energy density of the pulsed laser light is set to be 6 kHz and the number of the film needles irradiated with the pulsed laser light is set to 6 times, as shown in the photograph 12, 1 〇唧 can be produced. 2 〇 addition, microcrystalline. The crystallization ratio was evaluated by Raman spectrometry and found to be 〇°/〇. In addition, even if the pulse frequency is set to 8_, the same result is obtained, and 22 201034082 (Example 5) The energy density of the pulsed laser light is set to 16 〇 mJ/cm 2 and the pulse frequency is set to 6 kHz. When the film having the pulsed laser light is irradiated, if the number of shots is set to six, as shown in the photograph 13, microcrystals of 20 nm to 30 nm can be produced. The crystallization ratio was evaluated by Raman spectrometry and found to be 90%. In addition, the same result was obtained even if the pulse frequency was set to 8 kHz. (Example 6) A film in which the energy density of the pulsed laser light is 180 mJ/cm 2 and the pulse frequency is 6 kHz and the pulsed laser light is irradiated, and if the number of shots is set to 6 times, then As shown in Photo 14, microcrystals of 20 nm to 30 nm can be produced. The crystallization ratio was evaluated by Raman spectrometry and found to be 95%. In addition, the same result was obtained even if the pulse frequency was set to 8 kHz. (Example 7) A film in which the energy density of pulsed laser light is 200 mJ/cm2 and the pulse frequency is 6 kHz and the pulsed laser light is irradiated, if the number of shots is set to 6 times, then As shown in Fig. 15, microcrystals of 40 nm to 5 〇 nm can be produced. The crystallization ratio was evaluated by Raman spectrometry and found to be 95%. In addition, the same result was obtained even if the pulse frequency was set to 8 kHz. " (Comparative Example 1) A film in which the energy density of the pulsed laser light is 250 mJ/cm2 and the pulse frequency is 6 kHz and the pulsed laser light is irradiated, if 23 201034082 Λ ^L/ΛΧ When the number was set to 6 times, as shown in the photograph 16, the temperature was heated to a temperature exceeding the melting point to become a molten crystal, and uniform crystals were not obtained. The crystallization ratio was evaluated by Raman spectrometry and found to be 97%. In addition, the same result was obtained even if the number of shots was reduced to one. (Comparative Example 2) A film in which the energy density of the pulsed laser light is 26 〇mJ/cm 2 and the pulse frequency is 6 kHz and the pulsed laser light is irradiated, and if the number of shots is set to 6 times, then Photograph 17 shows the stripping of the surname. (Comparative Example 3) © A film in which the pulsed laser light has an energy density of 12 〇mj/cm 2 and a pulse frequency of 8 kHz and the pulsed laser light is irradiated, and if the number of shots is set to 8 times, Although crystallized, if gecc〇etching is performed, as shown in the photograph 18, some portions of the crystal are etched. The crystallization ratio was evaluated by Raman spectrometry and found to be 54%. (Example 8) A film in which the energy density of the pulsed laser light is 160 mJ/cm 2 and the pulse frequency is 8 kHz and the pulsed laser light is irradiated, and if the number of bursts is set to 2 times, then As shown in Fig. 19, microcrystals of 10 nm to 2 〇 nm can be produced. The crystallization ratio was evaluated by Raman spectrometry and found to be 75%. (Example 9) A film in which the energy density of the pulsed laser light is 180 mj/cm 2 and the pulse frequency is 8 kHz and the pulsed laser light is irradiated, and if the number of shots is set to 2 times, then as shown in the photograph 20 The microcrystals shown can be made from 1〇nm~20 nm 24 201034082. The crystallization ratio was evaluated by Raman spectrometry, and the result was 78%. , 'Ma (Comparative Example 4) The same experiment was carried out using a XeCl excimer laser having a wavelength of 308 nm and a pulse width of 20 nsec different from the above experiment. A film in which the energy density of the pulsed laser light is 180 mJ/cm 2 and the pulse frequency is 300 Hz and the pulsed laser light is irradiated, and the film is crystallized 8 times, and then SEM is performed. When Secco etching is performed for observation, all the portions are etched. The crystallization ratio was evaluated by Raman spectrometry and found to be 54%. It is generally considered that the reason is that only the surface layer is crystallized due to the short wavelength. (Comparative Example 5) The same experiment was carried out using a Xeci excimer laser having a wavelength of 308 nm and a pulse width of 20 nsec different from the above experiment. A film in which the energy density of the pulsed laser light is 200 mJ/cm 2 and the pulse frequency is 3 Hz and the pulsed laser light is irradiated is set to 8 times as shown in the photograph 21. The film was heated to a temperature exceeding the melting point of the crystal to become a molten crystal, and uniform crystals were not obtained. The crystallization ratio was evaluated by Raman spectrometry and found to be 97%. [Table 2] 25 201034082 26 State grain size (nm) I Crystallinity (%) | SEM photo number (shot) Energy density (mJ/cm2) Pulse frequency|wavelength/pulse width test material No. 1 0s ^ > Photo 18 〇〇1—» 8 kHz |355 nm/80 ns Ui |Comparative example Microcrystallization 10 to 20 00 |Photo 10 | 6 kHz 355 nm/80 ns K3 Example Microcrystallization 10 to 20 00 00 | Photo 11 | 〇 \ OJ Fine Crystallization 10 ~ 20 Name I Photo 12 ! 〇 \ Private Micro Crystallization 20 〜 30 | Photo 13 1 〇 \ S Fine Crystallization 10 〜 20 ΰί | Photo 19 IK) t—* s 8 kHz 00 Fine crystallization 10 〜 20 | Photo 20 | KJ g VO Fine crystallization 20 〜 30 \〇Lh | Photo 14 j 〇 \ 1—k tx 6 kHz ON Fine crystallization 40 〜 50 \〇 "Photo 15 1 〇 \ to o -J Melt crystallization greater than or equal to 100 Factory photo 16 1 〇\ NJ 6 kHz 355 nm/80 ns »—» Comparative Example Erosion 1 | Photo 17 | Os K) g K) Sm gl according to 1 〇〇g 300 Hz 308 nm / 20 ns private molten crystal 1 VO | Photo 21 1 〇〇o KJi 339.12pif 201034082 7 This: = the average particle size of the work is 15 her, the standard test is 7 = comparison i, 'an average grain size of coffee 72, a standard deviation of 42 nm square opening
如圖5與圖3、圖4的照片明顯可知 β 的多結㈣薄膜’其晶粒的不均小且結晶率的比例亦^ 進而可確認本發明的多結_薄膜於面整體上均質地多沾 晶化’雷射的重合部亦生成相同的結晶。晶粒為小於等^ 50 nm，較小，亦未產生突起，均勻地獲得結晶質矽膜、 因此可提供TFT特性的不均少的石夕膜。 以上，已基於上述實施形態以及實例對本發明進行了 說明，但本發明並不限定於上述說明的範圍，只要不脫離 本發明的範圍，則當然可加以適當變更。 雖然本發明已以較佳實施例揭露如上，然其並非用以 限定本發明，任何熟習此技藝者，在不脫離本發明之精神 和範圍内，當可作些許之更動與潤飾，因此本發明之保護 範圍當視後附之申請專利範圍所界定者為准。 【圖式簡單說明】 圖1是表示本發明的一實施形態的製造裝置即紫外線 固體雷射退火處理裝置的縱剖面圖。 圖2同為表示在實例中改變製造條件而照射脈衝雷射 之後的薄膜的SEM照片。 圖3同為表示在其他實例中改變製造條件而照射脈衝 雷射之後的薄膜的SEM照片。 圖4同為表示在其他實例中改變製造條件而照射脈衝 27 201034082 雷射之後的的薄膜的SEM照片。 圖5是表示拉曼分光測定結果的圖。 【主要元件符號說明】 1 :紫外線固體雷射退火處理裝置 2:紫外線固體雷射振盪器 2a :控制電路 3 :衰減器（減弱器） 4 :結合器As is apparent from the photographs of Fig. 5, Fig. 3, and Fig. 4, the multi-junction (tetra) film of β has a small crystal grain size and a ratio of crystallinity. Further, it can be confirmed that the multi-junction of the present invention is uniform in the entire surface. The multi-stained crystallized 'laser overlap' also produces the same crystals. When the crystal grains are smaller than or equal to 50 nm, the protrusions are not generated, and the crystalline ruthenium film is uniformly obtained, so that the ruthenium film having less unevenness in TFT characteristics can be provided. The present invention has been described above based on the above-described embodiments and examples, but the present invention is not limited to the scope of the invention, and may be appropriately modified without departing from the scope of the invention. While the present invention has been described in its preferred embodiments, the present invention is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a longitudinal sectional view showing an ultraviolet solid-state laser annealing treatment apparatus which is a manufacturing apparatus according to an embodiment of the present invention. Fig. 2 is also a SEM photograph showing a film after irradiating a pulsed laser by changing manufacturing conditions in the examples. Fig. 3 is also a SEM photograph showing a film after irradiating a pulsed laser by changing manufacturing conditions in other examples. Fig. 4 is also a SEM photograph showing a film after the laser beam 27 201034082 is irradiated by changing the manufacturing conditions in other examples. Fig. 5 is a view showing the results of Raman spectrometry. [Main component symbol description] 1 : Ultraviolet solid laser annealing treatment device 2: Ultraviolet solid laser oscillator 2a : Control circuit 3 : Attenuator (weakener) 4 : Combiner
5 :光纖 6 :除振台 7:光學系統 8 :基板 8a:非晶矽薄膜 9:基板載置台 10 :掃描裝置 70a :聚光透鏡 70b:聚光透鏡 ❹ 71a :光束均勻器 71b :光束均勻器 285: Optical fiber 6: Vibration removing table 7: Optical system 8: Substrate 8a: Amorphous germanium film 9: Substrate mounting table 10: Scanning device 70a: Condenser lens 70b: Condenser lens ❹ 71a: Beam uniformizer 71b: Beam uniformity 28
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