TWI477632B - Boron doped zinc oxide sputtering target and its application - Google Patents
Boron doped zinc oxide sputtering target and its application Download PDFInfo
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- 238000005477 sputtering target Methods 0.000 title claims description 69
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims description 36
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims description 26
- 229910052796 boron Inorganic materials 0.000 title claims description 26
- 239000011787 zinc oxide Substances 0.000 title description 17
- JUGMVQZJYQVQJS-UHFFFAOYSA-N [B+3].[O-2].[Zn+2] Chemical compound [B+3].[O-2].[Zn+2] JUGMVQZJYQVQJS-UHFFFAOYSA-N 0.000 claims description 84
- 238000004544 sputter deposition Methods 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 35
- 230000008569 process Effects 0.000 claims description 30
- 239000011701 zinc Substances 0.000 claims description 18
- 238000002834 transmittance Methods 0.000 claims description 15
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 238000007747 plating Methods 0.000 claims 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 10
- JAONJTDQXUSBGG-UHFFFAOYSA-N dialuminum;dizinc;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Zn+2].[Zn+2] JAONJTDQXUSBGG-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 238000001755 magnetron sputter deposition Methods 0.000 description 6
- YGBGWFLNLDFCQL-UHFFFAOYSA-N boron zinc Chemical compound [B].[Zn] YGBGWFLNLDFCQL-UHFFFAOYSA-N 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910052733 gallium Inorganic materials 0.000 description 4
- 230000005693 optoelectronics Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- -1 among which Chemical compound 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000009694 cold isostatic pressing Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000001552 radio frequency sputter deposition Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000003232 water-soluble binding agent Substances 0.000 description 1
- AKVPCIASSWRYTN-UHFFFAOYSA-N zinc oxygen(2-) silicon(4+) Chemical compound [Si+4].[O-2].[Zn+2].[O-2].[O-2] AKVPCIASSWRYTN-UHFFFAOYSA-N 0.000 description 1
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- Physical Vapour Deposition (AREA)
- Compositions Of Oxide Ceramics (AREA)
Description
本發明係關於一種硼鋅氧化物濺鍍靶材，尤指一種可應用於直流濺鍍製程之硼鋅氧化物濺鍍靶材。此外，本發明另關於一種利用直流濺鍍製程形成硼鋅氧化物薄膜之方法及其硼鋅氧化物薄膜。The invention relates to a boron zinc oxide sputtering target, in particular to a boron zinc oxide sputtering target which can be applied to a DC sputtering process. Further, the present invention relates to a method of forming a boron zinc oxide film by a DC sputtering process and a boron zinc oxide film thereof.
透明導電氧化物(transparent conducting oxide,TCO)由於在可見光區域能夠具有大於80%以上之高透光性以及薄膜電阻率小於10 Ω/square之導電性，因而能夠被廣泛地應用於各種光電產品(例如：太陽能電池、平面顯示器、發光二極體等)中，成為一種良好的透明導電電極材料。Transparent conductive oxide (TCO) can be widely used in various optoelectronic products because it can have a high transmittance of more than 80% in the visible light region and a conductivity of less than 10 Ω/square. For example, in solar cells, flat-panel displays, light-emitting diodes, etc., it is a good transparent conductive electrode material.
傳統透明導電氧化物如：錫摻雜銦氧化物(tin doped indium oxide,ITO)(簡稱銦錫氧化物)或一氧化鋅(ZnO)等，其中，銦錫氧化物雖具備高透光性與良好的導電性之優點，卻因為銦元素原料短缺、價格昂貴以及容易和氫氣電漿產生還原反應等問題，而逐漸被其他透明導電氧化物所取代；而一氧化鋅雖無上述諸多缺點，卻因為無法提供足夠的導電性，而降低其於光電產業之應用價值。Conventional transparent conductive oxides such as tin doped indium oxide (ITO) (indium tin oxide) or zinc oxide (ZnO), among which, indium tin oxide has high light transmittance and The advantages of good electrical conductivity are gradually replaced by other transparent conductive oxides due to shortage of indium raw materials, high cost, and easy reduction reaction with hydrogen plasma. However, zinc oxide does not have many of the above disadvantages, but Because it can not provide enough conductivity, it reduces its application value in the optoelectronic industry.
因此，為了提升一氧化鋅的導電性，通常會在一氧化鋅中摻雜如硼、鋁或鎵等元素，形成硼摻雜鋅氧化物(boron doped zinc oxide,BZO)(簡稱硼鋅氧化物)、鋁摻雜鋅氧化物(aluminum doped zinc oxide,AZO)(簡稱鋁鋅氧化物)或鎵摻雜鋅氧化物(gallium doped zinc oxide,GZO)(簡稱鎵鋅氧化物)等透明導電氧化物。透過摻雜元素置換鋅的晶格位 置，使得BZO、AZO或GZO獲得所需之導電性(即，薄膜電阻率低於10 Ω/square)，而可應用於各種光電產品中。Therefore, in order to improve the conductivity of zinc oxide, an element such as boron, aluminum or gallium is usually doped into zinc oxide to form boron doped zinc oxide (BZO) (abbreviated as boron zinc oxide). ), transparent doped zinc oxide (AZO) (abbreviated as aluminum zinc oxide) or gallium doped zinc oxide (GZO) (referred to as gallium zinc oxide) and other transparent conductive oxide . Replacement of the lattice position of zinc through doping elements This allows BZO, AZO or GZO to achieve the desired conductivity (ie, film resistivity below 10 Ω/square) and can be used in a variety of optoelectronic products.
根據Jun-chi Nomoto et.al., J.Vac.Sci.Technol.,A29 ,041504(2011)文獻報導指出，以直流磁控濺鍍製程(direct current magnetron sputtering,dc-MS sputtering)製作硼鋅氧化物薄膜，其薄膜電阻率、霍爾遷移率(Hall mobility)及載子濃度的變異性很大；若以射頻磁控濺鍍製程(radio frequency magnetron sputtering,rf-MS sputtering)製作硼鋅氧化物薄膜，則不會有上述問題。According to Jun-chi Nomoto et.al., J.Vac.Sci.Technol., A 29 ,041504 (2011), it is reported that boron is produced by direct current magnetron sputtering (dc-MS sputtering). Zinc oxide film has great variability in film resistivity, Hall mobility and carrier concentration; if boron-zinc is produced by radio frequency magnetron sputtering (rf-MS sputtering) The oxide film does not have the above problems.
此外，由於形成硼鋅氧化物濺鍍靶材所使用的兩種氧化物中，三氧化二硼容易隨著溫度的升高而揮發，不僅使得於製程中難以控制硼的添加量，對於硼鋅氧化物濺鍍靶材中的硼含量更是難以掌握。In addition, among the two oxides used to form the borozinc oxide sputtering target, the boron trioxide tends to volatilize as the temperature increases, which makes it difficult to control the amount of boron added in the process. The boron content in the oxide sputtering target is even more difficult to grasp.
是以，現有技術的硼鋅氧化物濺鍍靶材於濺鍍形成硼鋅氧化物薄膜時，僅能採用濺鍍速率較慢的射頻磁控濺鍍製程形成硼鋅氧化物薄膜，而無法採用直流磁控濺鍍製程形成成分均勻的硼鋅氧化物薄膜。此外，目前也沒有相關文獻報導提及，硼鋅氧化物濺鍍靶材可採用具備高濺鍍速率且製程條件易於控制的直流濺鍍製程，形成可應用於光電產品之透明導電電極的硼鋅氧化物薄膜。Therefore, the prior art boron-zinc oxide sputtering target can only form a boron-zinc oxide film by using a radio frequency magnetron sputtering process with a slow sputtering rate when a boron-zinc oxide film is formed by sputtering. The DC magnetron sputtering process forms a uniform composition of boron zinc oxide film. In addition, there is no relevant literature report at present, the boron-zinc oxide sputtering target can adopt a DC sputtering process with high sputtering rate and easy control of process conditions to form boron zinc which can be applied to transparent conductive electrodes of photoelectric products. Oxide film.
有鑒於現有技術所面臨之問題，本發明之主要目的在於提供一種硼鋅氧化物濺鍍靶材，其能採用高濺鍍速率且製程條件易於控制的直流濺鍍製程(DC sputtering)形成硼鋅氧化物薄膜，藉以提升硼鋅氧化物薄膜之製程產率，並 且獲得具有良好薄膜特性之硼鋅氧化物薄膜。In view of the problems faced by the prior art, the main object of the present invention is to provide a boron-zinc oxide sputtering target capable of forming boron zinc by a DC sputtering process with high sputtering rate and easy control of process conditions. An oxide film for improving the process yield of the boron zinc oxide film, and And a boron zinc oxide film having good film properties is obtained.
為達成前述目的，本發明提供一種硼鋅氧化物濺鍍靶材(boron doped zinc oxide sputtering target,BZO sputtering target)，其中硼含量相對於硼與鋅之含量和係介於1.15原子百分比至6.74原子百分比，且該硼鋅氧化物濺鍍靶材中包含一基底相及一二次相，該二次相之面積係佔硼鋅氧化物濺鍍靶材之面積的2%至25%。In order to achieve the above object, the present invention provides a boron doped zinc oxide sputtering target (BZO sputtering target), wherein the boron content is between 1.15 atomic percent and 6.74 atoms relative to the boron and zinc content. Percentage, and the borozinc oxide sputtering target comprises a base phase and a secondary phase, the secondary phase having an area of 2% to 25% of the area of the borozinc oxide sputtering target.
本發明將硼鋅氧化物靶材中的二次相面積控制於適當的範圍內，使所述之硼鋅氧化物濺鍍靶材可採用直流濺鍍製程，形成具備良好薄膜特性之硼鋅氧化物薄膜。The invention controls the secondary phase area in the boron zinc oxide target to an appropriate range, so that the boron zinc oxide sputtering target can adopt a direct current sputtering process to form a boron zinc oxide having good film characteristics. Film.
較佳的，所述二次相之面積係佔硼鋅氧化物濺鍍靶材之面積的5.5%至16%。Preferably, the area of the secondary phase is 5.5% to 16% of the area of the borozinc oxide sputtering target.
較佳的，於本發明硼鋅氧化物濺鍍靶材中，基底相之成份係為一氧化鋅，二次相之成份係為Zn(3+y) B(2-x) O6 ，其中x係介於0至0.5之間，y係介於0至1.5之間。其中，該二次相成分例如：Zn3.6 B1.6 O6 、Zn4.1 B1.9 O6 、Zn4.4 B1.9 O6 。Preferably, in the borosilicate sputtering target of the present invention, the component of the base phase is zinc oxide, and the composition of the secondary phase is Zn (3+y) B (2-x) O 6 , wherein The x series is between 0 and 0.5 and the y is between 0 and 1.5. The secondary phase component is, for example, Zn 3.6 B 1.6 O 6 , Zn 4.1 B 1.9 O 6 , Zn 4.4 B 1.9 O 6 .
較佳的，於本發明硼鋅氧化物濺鍍靶材中，二次相之成份係為Zn(3+y) B(2-x) O6 ，y=3/2x。更佳的，當y=3/2x時，x係介於0至0.5之間，y係介於0至0.75之間。Preferably, in the boron zinc oxide sputtering target of the present invention, the composition of the secondary phase is Zn (3+y) B (2-x) O 6 and y=3/2x. More preferably, when y=3/2x, the x is between 0 and 0.5 and the y is between 0 and 0.75.
較佳的，於本發明硼鋅氧化物濺鍍靶材中，可進一步包含有至少一摻雜元素，該摻雜元素係選自於由下列所組成之群組：鋁、鎵、銦、鍺、矽及錫。較佳的，該至少一摻雜元素之含量和相對於硼與鋅之含量和係介於0.25至0.5原子百分比之間。Preferably, in the borozinc oxide sputtering target of the present invention, at least one doping element may be further included, and the doping element is selected from the group consisting of aluminum, gallium, indium, and antimony. , bismuth and tin. Preferably, the content of the at least one doping element and the content of the boron and zinc are between 0.25 and 0.5 atomic percent.
較佳的，本發明硼鋅氧化物濺鍍靶材之絕對密度係為 5.2g/cm3 以上。Preferably, the boron zinc oxide sputtering target of the present invention has an absolute density of 5.2 g/cm 3 or more.
為達成前述目的，本發明另提供一種利用直流濺鍍製程形成硼鋅氧化物薄膜之方法，其係使用前述之硼鋅氧化物濺鍍靶材，利用直流濺鍍製程於一基板上濺鍍形成該硼鋅氧化物薄膜。In order to achieve the above object, the present invention further provides a method for forming a boron zinc oxide film by using a DC sputtering process, which uses the foregoing boron zinc oxide sputtering target to form a sputtering process on a substrate by a DC sputtering process. The boron zinc oxide film.
較佳的，該直流濺鍍製程之工作壓力係介於1.7至9毫托(mTorr)之間，直流濺鍍功率密度係介於0.55至7 W/cm2 之間，且基板的溫度係維持於25℃至350℃之間。Preferably, the DC sputtering process has a working pressure of between 1.7 and 9 milliTorr (mTorr), a DC sputtering power density of between 0.55 and 7 W/cm 2 , and the substrate temperature is maintained. Between 25 ° C and 350 ° C.
為達成前述目的，本發明再提供一種硼鋅氧化物薄膜，其係使用如前述之任一硼鋅氧化物濺鍍靶材所濺鍍而成，且該硼鋅氧化物薄膜中硼含量相對於硼與鋅之含量和係介於1原子百分比至6原子百分比，且該硼鋅氧化物薄膜之電阻率係介於1×10-3 至9×10-3 Ω-cm之間，且光波長400 nm至1100 nm之平均光穿透率係介於80%至93%。In order to achieve the foregoing object, the present invention further provides a boron zinc oxide film which is sputtered using any of the foregoing boron zinc oxide sputtering targets, and the boron content in the boron zinc oxide film is relative to The content of boron and zinc is between 1 atomic percent and 6 atomic percent, and the resistivity of the boron zinc oxide film is between 1×10 −3 and 9×10 −3 Ω-cm, and the wavelength of light The average light transmittance from 400 nm to 1100 nm is between 80% and 93%.
較佳的，該硼鋅氧化物薄膜，其硼含量相對於硼與鋅之含量和係介於1原子百分比至6原子百分比，且該硼鋅氧化物薄膜之電阻率係介於1×10-3 至7×10-3 Ω-cm之間，且光波長400 nm至1100 nm之平均光穿透率係介於89%至92%。Preferably, the boron zinc oxide film has a boron content of from 1 atomic percent to 6 atomic percent relative to the boron and zinc content, and the boron zinc oxide film has a resistivity of 1×10 − The average light transmittance between 3 and 7 × 10 -3 Ω-cm and the light wavelength of 400 nm to 1100 nm is between 89% and 92%.
所述之硼鋅氧化物薄膜可採用各種濺鍍製程所濺鍍而成，例如：直流濺鍍製程、直流磁控濺鍍製程、脈衝直流濺鍍製程、射頻濺鍍製程或射頻磁控濺鍍製程，但並非僅限於此。The borozide oxide film can be sputtered by various sputtering processes, such as DC sputtering process, DC magnetron sputtering process, pulsed DC sputtering process, RF sputtering process or RF magnetron sputtering. Process, but not limited to this.
較佳的，本發明硼鋅氧化物薄膜係使用前述之任一硼鋅氧化物濺鍍靶材，並且經由直流濺鍍製程所濺鍍而成。較佳 的，本發明硼鋅氧化物薄膜係使用如前述之方法所形成。Preferably, the boron zinc oxide film of the present invention is formed by sputtering a target using any of the foregoing boron zinc oxide sputtering targets. Better The boron zinc oxide film of the present invention is formed by the method described above.
綜上所述，本發明提供一種硼鋅氧化物濺鍍靶材，藉由控制該濺鍍靶材之二次相面積範圍，使其能夠採用高濺鍍速率與製程條件容易控制的直流濺鍍製程，濺鍍形成具有良好薄膜特性的硼鋅氧化物薄膜，進而提升硼鋅氧化物薄膜之製程產率。In summary, the present invention provides a boron-zinc oxide sputtering target, which can control DC sputtering which is easily controlled by high sputtering rate and process conditions by controlling the secondary phase range of the sputtering target. The process, sputtering, forms a boron-zinc oxide film having good film properties, thereby improving the process yield of the boron-zinc oxide film.
以下，將藉由具體實施例說明本發明之實施方式，熟習此技藝者可經由本說明書之內容輕易地了解本發明所能達成之優點與功效，並且於不悖離本發明之精神下進行各種修飾與變更，以施行或應用本發明之內容。In the following, the embodiments of the present invention will be described by way of specific examples, and those skilled in the art can readily understand the advantages and functions of the present invention, and can carry out various kinds without departing from the spirit of the present invention. Modifications and variations are made to implement or apply the subject matter of the invention.
首先，提供三氧化二硼(B2 O3 )粉末、一氧化鋅(ZnO)粉末，並將三氧化二硼粉末、一氧化鋅粉末、陰離子型分散劑及水均勻混合，以形成一漿料。以三氧化二硼粉末及一氧化鋅粉末之總和為100重量百分比，實施例1至3中三氧化二硼粉末與一氧化鋅粉末之混合比例係如下表1所示。First, a boron trioxide (B 2 O 3 ) powder, a zinc oxide (ZnO) powder, and a boron trioxide powder, a zinc oxide powder, an anionic dispersant, and water are uniformly mixed to form a slurry. . The mixing ratio of the boron trioxide powder and the zinc oxide powder in Examples 1 to 3 was as shown in Table 1 below, based on 100% by weight of the total of the boron trioxide powder and the zinc oxide powder.
接著，將前述之漿料與水溶性黏結劑均勻混合，再以噴霧方式形成約60微米的造粒粉末。Next, the slurry was uniformly mixed with a water-soluble binder, and a granulated powder of about 60 μm was formed by spraying.
之後，將前述步驟所獲得之混合粉末均勻充填於石墨模具後，依序經過冷壓(cold press,CP)及冷等靜壓法(cold isostatic pressing,CIP)進行預成型。Thereafter, the mixed powder obtained in the above step was uniformly filled in a graphite mold, and then subjected to preforming by cold press (CP) and cold isostatic pressing (CIP).
最後，將預成型之混合粉末與石墨模具置於800℃至130℃下燒結5至20小時，即獲得本發明之硼鋅氧化物濺鍍靶材。Finally, the preformed mixed powder and the graphite mold are sintered at 800 ° C to 130 ° C for 5 to 20 hours to obtain the boron zinc oxide sputtering target of the present invention.
本發明分別以光學顯微鏡(optical microscope,OM)、掃描式電子顯微鏡(scanning electronic microscope,SEM)及背向散射電子顯微鏡(back scattered electron microscope,BSE microscope)觀察實施例1至3之硼鋅氧化物濺鍍靶材的微結構。In the present invention, the boron Zn oxides of Examples 1 to 3 were observed by an optical microscope (OM), a scanning electron microscope (SEM), and a back scattered electron microscope (BSE microscope). The microstructure of the sputter target.
請參閱圖1A至圖1C、圖2A至圖2C及圖3A至圖3C所示，其係分別為實施例1至3之硼鋅氧化物濺鍍靶材的光學顯微鏡、掃描式電子顯微鏡及背向散射電子顯微鏡影像圖，圖中箭頭所指即為本發明硼鋅氧化物濺鍍靶材之二次相的分佈區域。本發明係採用電子微探儀Electron Probe X-ray MicroAnalyzer(EPMA)鑑定該硼鋅氧化物濺鍍靶材中二次相的成份，其結果係如下表2所示。1A to 1C, 2A to 2C, and 3A to 3C, which are optical microscopes, scanning electron microscopes A scattering electron microscope image, the arrow in the figure indicates the distribution area of the secondary phase of the boron-zinc oxide sputtering target of the present invention. In the present invention, the composition of the secondary phase in the boron-zinc oxide sputtering target is identified by an electron micro-inspector Electron Probe X-ray MicroAnalyzer (EPMA), and the results are shown in Table 2 below.
此外，另經由Image-pro plus 6.3影像分析軟體分析本發明硼鋅氧化物濺鍍靶材中二次相佔硼鋅氧化物濺鍍靶材之面積比例，其係使用掃描式電子顯微鏡影像圖之色差做對比度及明亮度之調整，使硼鋅氧化物濺鍍靶材之二次相與其周圍的一氧化鋅基底相在影像上產生明顯的差異，再經由Image-pro plus 6.3影像分析軟體判斷二次相之區域，並且藉由二次相面積佔整體處理後影像圖之面積比例推算 其二次相之面積百分比。請參閱圖1D至圖3D所示，圖中箭頭所指亦為本發明硼鋅氧化物濺鍍靶材之二次相的分佈區域。各實施例之硼鋅氧化物濺鍍靶材的基底相成分、二次相成分與濺鍍靶材之絕對密度之結果亦如下表2所示。In addition, the area ratio of the secondary phase to the boron-zinc oxide sputtering target in the boron-zinc oxide sputtering target of the present invention is analyzed by Image-pro plus 6.3 image analysis software, and the scanning electron microscope image is used. The color difference is adjusted for contrast and brightness, so that the secondary phase of the boron-zinc oxide sputtering target and the surrounding zinc oxide substrate phase have obvious differences in image, and then judged by Image-pro plus 6.3 image analysis software. The area of the secondary phase, and the ratio of the area of the secondary phase to the area of the image after processing The area percentage of the secondary phase. Referring to FIG. 1D to FIG. 3D, the arrows indicate the distribution area of the secondary phase of the boron-zinc oxide sputtering target of the present invention. The results of the base phase composition, the secondary phase composition, and the absolute density of the sputtering target of the borozinc oxide sputtering target of each example are also shown in Table 2 below.
使用本發明實施例1至實施例3之硼鋅氧化物濺鍍靶材，以工作壓力為3至5 mtorr下，在170℃之玻璃基板上濺鍍形成厚度約1000 nm之硼鋅氧化物薄膜，以不同的濺鍍功率所濺鍍而成之硼鋅氧化物薄膜。各實施例之硼鋅氧化物薄膜之薄膜電阻率與透光率之測試結果係如表3所示。Using the boron zinc oxide sputtering target of the first embodiment to the third embodiment of the present invention, a boron-zinc oxide film having a thickness of about 1000 nm is formed by sputtering on a glass substrate of 170 ° C at a working pressure of 3 to 5 mtorr. A boron-zinc oxide film sputtered with different sputtering powers. The test results of the film resistivity and light transmittance of the boro-zinc oxide film of each example are shown in Table 3.
請參閱圖4所示，利用本發明實施例1之硼鋅氧化物濺鍍靶材，以2.2 W/cm2 之直流濺鍍功率密度所濺鍍而成之硼鋅氧化物薄膜，該硼鋅氧化物薄膜中硼含量相對於硼與鋅之含量和係介於1.5至2.5原子百分比之間，其硼鋅氧化物薄膜可具有1.8×10-3 Ω-cm之電阻率，且其於400 nm至1100奈米之光波長下的平均光穿透率約為91.6%。Referring to FIG. 4, a boron zinc oxide film which is sputtered by a DC sputtering power density of 2.2 W/cm 2 using the boron zinc oxide sputtering target of the embodiment 1 of the present invention, the boron zinc The boron content in the oxide film is between 1.5 and 2.5 atomic percent relative to the boron and zinc content, and the boron zinc oxide film may have a resistivity of 1.8 × 10 -3 Ω-cm and is at 400 nm. The average light transmittance at a wavelength of light up to 1100 nm is about 91.6%.
使用本發明實施例2之硼鋅氧化物濺鍍靶材，分別以1.1、2.2及3.8W/cm2 之直流濺鍍功率密度所濺鍍而成之硼鋅氧化物薄膜，該硼鋅氧化物薄膜中硼含量相對於硼與鋅之含量和係介於3.7至4.1原子百分比之間，各硼鋅氧化物薄膜之電阻率分別為2.93×10-3 Ω-cm、2.31×10-3 Ω-cm及2.48×10-3 Ω-cm，且於400至1100奈米之光波長下的平均光穿透率約為89.9%、89.5%及89.7%。A boron zinc oxide film which is sputtered at a DC sputtering power density of 1.1, 2.2, and 3.8 W/cm 2 using the boron zinc oxide sputtering target of Example 2 of the present invention, the boron zinc oxide film The boron content in the film is between 3.7 and 4.1 atomic percent relative to the boron and zinc content, and the resistivity of each of the boron zinc oxide films is 2.93×10 -3 Ω-cm and 2.31×10 -3 Ω, respectively. Cm and 2.48 x 10 -3 Ω-cm, and the average light transmittance at a wavelength of light of 400 to 1100 nm is about 89.9%, 89.5%, and 89.7%.
使用本發明實施例3之硼鋅氧化物濺鍍靶材，分別以1.1 W/cm2 、1.6 W/cm2 及2.2 W/cm2 之直流濺鍍功率密度所濺鍍而成之硼鋅氧化物薄膜，該硼鋅氧化物薄膜中硼含量相對於硼與鋅之含量和係介於4.1至5.0之間，各硼鋅氧化物薄膜之電阻率分別為6.88×10-3 Ω-cm、6.83×10-3 Ω-cm及6.61 ×10-3 Ω-cm，且於400至1100奈米之光波長下的平均光穿透 率約為90.5%、90.3%及90.2%。The boron zinc oxide sputtering target of the embodiment 3 of the present invention is oxidized by boron zinc sputtering by sputtering at a power density of 1.1 W/cm 2 , 1.6 W/cm 2 and 2.2 W/cm 2 , respectively. The film has a boron content in the boron-zinc oxide film of between 4.1 and 5.0, and a resistivity of each of the boron-zinc oxide films of 6.88×10 -3 Ω-cm and 6.83, respectively. ×10 -3 Ω-cm and 6.61 × 10 -3 Ω-cm, and the average light transmittance at a light wavelength of 400 to 1100 nm is about 90.5%, 90.3%, and 90.2%.
於本比較例之鋁鋅氧化物濺鍍靶材中，以整體氧化物粉末之總量為100wt%，一氧化鋅含量係為98wt%，且三氧化二鋁之含量係為2wt%。In the aluminum zinc oxide sputtering target of the comparative example, the total amount of the integral oxide powder was 100% by weight, the zinc oxide content was 98% by weight, and the content of the aluminum oxide was 2% by weight.
接著，使用前述之鋁鋅氧化物濺鍍靶材，以工作壓力為3 mtorr下，功率密度2.2 W/cm2 ，在約170℃之玻璃基板上濺鍍形成厚度約1000 nm之鋁鋅氧化物薄膜。Next, using the aluminum zinc oxide sputtering target described above, a silicon zinc oxide having a thickness of about 1000 nm is sputtered on a glass substrate of about 170 ° C at a working pressure of 3 mtorr and a power density of 2.2 W/cm 2 . film.
請參閱圖5A及5B所示，於光波長介於400 nm至700 nm之光照下，使用本發明實施例1至3之硼鋅氧化物濺鍍靶材所濺鍍而成之硼鋅氧化物薄膜可具有如鋁鋅氧化物薄膜之光穿透率；且於光波長超過700 nm之光照下，本發明硼鋅氧化物薄膜可具有優於鋁鋅氧化物薄膜之光穿透率。Referring to FIGS. 5A and 5B, the boron-zinc oxide film is sputtered using the boron-zinc oxide sputtering target of the first to third embodiments of the present invention under illumination of a wavelength of 400 nm to 700 nm. The borophosphor oxide film of the present invention may have a light transmittance higher than that of the aluminum zinc oxide film at a light transmittance such as an aluminum zinc oxide film; and under illumination of a light wavelength exceeding 700 nm.
實驗結果顯示，本發明之硼鋅氧化物濺鍍靶材可順利經由高濺鍍速率之直流濺鍍製程，於400 nm至1100 nm之光波長下獲得80%以上之高透光性以及低於10-2 Ω-cm以下之導電性的硼鋅氧化物薄膜。The experimental results show that the boron-zinc oxide sputtering target of the present invention can smoothly obtain a high transmittance of 80% or more and a low transmittance at a light wavelength of 400 nm to 1100 nm through a high-sputtering rate DC sputtering process. Conductive boron zinc oxide film of 10 -2 Ω-cm or less.
上述實施例僅係為了方便說明而舉例而已，本發明所主張之權利範圍自應以申請專利範圍所述為準，而非僅限於上述實施例。The above-mentioned embodiments are merely examples for convenience of description, and the scope of the claims is intended to be limited to the above embodiments.
圖1A係為本發明實施例1之硼鋅氧化物濺鍍靶材的光學影像圖。1A is an optical image diagram of a boron zinc oxide sputtering target according to Embodiment 1 of the present invention.
圖1B係為本發明實施例1之硼鋅氧化物濺鍍靶材的掃描式電子顯微鏡影像圖。1B is a scanning electron microscope image of a boron zinc oxide sputtering target according to Embodiment 1 of the present invention.
圖1C係為本發明實施例1之硼鋅氧化物濺鍍靶材的背向散射電子影像圖。1C is a backscattered electron image of a boron zinc oxide sputtering target according to Embodiment 1 of the present invention.
圖1D係為本發明實施例1之硼鋅氧化物濺鍍靶材經Image-pro plus 6.3影像分析軟體分析之影像結果圖。1D is a view showing the image of the boron-zinc oxide sputtering target of the first embodiment of the present invention subjected to Image-pro plus 6.3 image analysis software analysis.
圖2A係為本發明實施例2之硼鋅氧化物濺鍍靶材的光學影像圖。2A is an optical image diagram of a boron zinc oxide sputtering target according to Embodiment 2 of the present invention.
圖2B係為本發明實施例2之硼鋅氧化物濺鍍靶材的掃描式電子顯微鏡影像圖。2B is a scanning electron microscope image of a boron-zinc oxide sputtering target according to Embodiment 2 of the present invention.
圖2C係為本發明實施例2之硼鋅氧化物濺鍍靶材的背向散射電子影像圖。2C is a backscattered electron image of a boron zinc oxide sputtering target according to Embodiment 2 of the present invention.
圖2D係為本發明實施例2之硼鋅氧化物濺鍍靶材經Image-pro plus 6.3影像分析軟體之影像結果圖。2D is a view showing the image of the boron-zinc oxide sputtering target of the embodiment 2 of the present invention subjected to Image-pro plus 6.3 image analysis software.
圖3A係為本發明實施例3之硼鋅氧化物濺鍍靶材的光學影像圖。3A is an optical image diagram of a boron zinc oxide sputtering target according to Embodiment 3 of the present invention.
圖3B係為本發明實施例3之硼鋅氧化物濺鍍靶材的掃描式電子顯微鏡影像圖。3B is a scanning electron microscope image of a boron-zinc oxide sputtering target according to Embodiment 3 of the present invention.
圖3C係為本發明實施例3之硼鋅氧化物濺鍍靶材的背向散射電子影像圖。3C is a backscattered electron image of the boron zinc oxide sputtering target of Example 3 of the present invention.
圖3D係為本發明實施例3之硼鋅氧化物濺鍍靶材經Image-pro plus 6.3影像分析軟體分析之影像結果圖。FIG. 3D is a view showing the image of the boron-zinc oxide sputtering target of the embodiment 3 of the present invention subjected to Image-pro plus 6.3 image analysis software analysis.
圖4係為使用本發明實施例1至3之硼鋅氧化物濺鍍靶材經由直流濺鍍製程所獲得之硼鋅氧化物薄膜，其薄膜之電阻率及平均光穿透率與直流濺鍍功率密度之關係圖。4 is a boro-zinc oxide film obtained by a DC sputtering process using the boro-zinc oxide sputtering target of Examples 1 to 3 of the present invention, the resistivity and average light transmittance of the film and DC sputtering. Power density diagram.
圖5A及5B係為使用本發明實施例1至3之硼鋅氧化物濺鍍靶材及鋁鋅氧化物濺鍍靶材經由直流濺鍍製程所獲 得之硼鋅氧化物薄膜及鋁鋅氧化物薄膜，於不同光波長下薄膜光穿透率之關係圖。5A and 5B are obtained by using a DC sputtering process using the borozinc oxide sputtering target and the aluminum zinc oxide sputtering target of Embodiments 1 to 3 of the present invention. The relationship between the borophosphorus oxide film and the aluminum-zinc oxide film at different light wavelengths.
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