CN102874764A - 传感材料及其制备方法及实时传感方法 - Google Patents
传感材料及其制备方法及实时传感方法 Download PDFInfo
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- 239000011540 sensing material Substances 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 31
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 77
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 43
- 239000002071 nanotube Substances 0.000 claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 32
- 238000001354 calcination Methods 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 230000007935 neutral effect Effects 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 71
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical group [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 19
- 238000001228 spectrum Methods 0.000 claims description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 238000001069 Raman spectroscopy Methods 0.000 claims description 10
- 230000003287 optical effect Effects 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 4
- -1 2-ethyl hexyl Chemical group 0.000 claims description 3
- 101710134784 Agnoprotein Proteins 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 3
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 2
- 230000008676 import Effects 0.000 claims description 2
- QPPQHRDVPBTVEV-UHFFFAOYSA-N isopropyl dihydrogen phosphate Chemical compound CC(C)OP(O)(O)=O QPPQHRDVPBTVEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 abstract description 6
- 238000001914 filtration Methods 0.000 abstract description 5
- 239000012702 metal oxide precursor Substances 0.000 abstract description 3
- 238000005273 aeration Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 22
- 239000010949 copper Substances 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 17
- 239000000843 powder Substances 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 229910052802 copper Inorganic materials 0.000 description 11
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 10
- 229960004643 cupric oxide Drugs 0.000 description 8
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000005751 Copper oxide Substances 0.000 description 5
- 229910000431 copper oxide Inorganic materials 0.000 description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 5
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 4
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- DDYSHSNGZNCTKB-UHFFFAOYSA-N gold(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Au+3].[Au+3] DDYSHSNGZNCTKB-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 4
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000005622 photoelectricity Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 101001047746 Homo sapiens Lamina-associated polypeptide 2, isoform alpha Proteins 0.000 description 1
- 101001047731 Homo sapiens Lamina-associated polypeptide 2, isoforms beta/gamma Proteins 0.000 description 1
- 102100023981 Lamina-associated polypeptide 2, isoform alpha Human genes 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910007991 Si-N Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910006294 Si—N Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
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Abstract
本发明涉及传感材料及其制备方法及实时传感方法,该传感材料的制备方法包括以下步骤:(a)提供一金属氧化物前驱物的水溶液;(b)混合二氧化钛纳米管与金属氧化物前驱物的水溶液以形成一混合物;(c)以一弱碱调整混合物的pH值至中性;(d)将混合物分散于水中并加热;及(e)过滤混合物以留下固体部分,并在持续通氧的环境中锻烧固体部分,以形成负载一金属氧化物的二氧化钛纳米管。本发明还提供一种传感材料及应用该传感材料的实时传感方法,可侦测ppb至ppt等级的掺杂类气体。
Description
技术领域
本发明涉及一种传感材料,且特别涉及一种兆分之一(parts pertrillion,ppt)级的传感材料及其制备方法,以及应用此传感材料的实时传感方法。
背景技术
半导体与光电制造方法中使用的气体及其副产物可成为气态微量污染物(airborne molecular contaminant,AMC)而导致多种产品缺陷问题,其中典型的五大类气态微污染为酸性气体(molecular acids,MA)、碱性气体(molecular bases,MB)、气态可凝结物(molecular condensables,MC)、掺杂类气体(molecular dopants,MD)及未分类(no class,MO)。例如酸性气体会腐蚀金属层、碱性气体会产生T-topping的危害、气态可凝结物会影响薄膜特性(使Si-N膜转变为Si-O膜并使曝光机镜片雾化)、掺杂类气体(例如磷化氢(PH3)、砷化氢(AsH3))会导致半导体p-n电性偏移、未分类(no classes,MO)中的臭氧(O3)污染会使组件电容量降低。
为了避免微量污染物导致半导体与光电制造方法的产率下降,每年国家半导体技术蓝图委员会(International Technology Roadmap forSemiconductors,ITRS)会对不同线宽制造方法建议其污染物容许浓度。如上所述,磷化氢为气态微量污染物的一种,其在常温下为无色有毒气体,当吸入人体时更会造成呼吸困难甚至可能致死,因此半导体厂皆需依法安装磷化氢气体的侦测器。以45纳米(nm)制造方法为例,ITRS建议PH3浓度值应小于10兆分之一(parts per trillion,ppt),因此需要可侦测达到ppt等级浓度的气体侦测器。市面上所贩售的磷化氢气体侦测器主要为电化学式与色带式两种类型,两者的市场占有率高达9成以上,然而这些市售的磷化氢气体侦测器侦测下限约在100-10十亿分之一(parts per billion,ppb),远高于ITRS所建议的10ppt。目前业界采用的侦测掺杂类气体(MD)的方法是将测试晶圆暴露于洁净室24~48小时,然后以氢氟酸(HF)溶解测试晶圆表面所沉降的MD,最后再用电感耦合等离子体质谱分析仪(ICP-MS)进行定性、定量分析。此方法极耗费时间与人力,且每个MD样品的采样与分析时间长达2-7天,因此当确认遭受MD污染时,已历时数十天,导致数以万片的晶圆因遭受污染而报废,半导体厂也因此遭受数亿台币的损失。
中国台湾专利公开号201109081A1揭露一种负载金属氧化物的纳米结构材料及含磷化合物的检测方法,是以一种负载金属氧化物的纳米结构材料,经以下步骤合成传感材料:混合硅或钛氧化物与一界面活性剂,并聚合成一中孔洞(mesoporous)氧化硅或氧化钛,并进一步与一金属或金属化合物混合,最后对该混合物进行异相成核。根据另一实施例,负载金属氧化物的纳米结构材料的形成步骤也可为:将含硅或钛化合物与碳材模板一起进行锻烧,接着将所得产物与一金属或金属化合物混合,并进行第二次锻烧。此案还提供利用上述纳米结构材料所进行的含磷化合物(例如磷化氢)的检测方法。然而,此案所合成的传感材料需在400℃下的较高温进行监测,且对磷化氢的侦测下限仅达100-10ppb/6小时。
因此,亟需可实时侦测ppt级气态微量污染物的传感材料及传感方法。
发明内容
本发明提供一种传感材料的制备方法,包括以下步骤:(a)提供一金属氧化物前驱物的水溶液;(b)混合二氧化钛(TiO2)纳米管与该金属氧化物前驱物的水溶液以形成一混合物;(c)以一弱碱调整该混合物的pH值至中性;(d)将该混合物分散于水中并加热;及(e)过滤该混合物以留下固体部分,并在持续通氧的环境中锻烧该固体部分,以形成负载一金属氧化物的二氧化钛纳米管。
本发明还提供一种传感材料,包括:二氧化钛(TiO2)纳米管;及均匀分散且负载于该二氧化钛纳米管上的金属氧化物,其中该负载金属氧化物的二氧化钛纳米管的比表面积(BET)约为200-400平方米/克(m2/g),且该金属氧化物的金属元素相对于钛元素的原子比例约为10-50%。
本发明还提供一种实时传感方法,包括:提供上述传感材料;导入一待测气体与该传感材料反应;及以拉曼光谱仪系统或傅立叶红外线光谱仪系统分析反应结果。
为让本发明的上述和其它目的、特征和优点能更明显易懂,下文特举出较佳实施例,并配合附图,作如下详细说明:
附图说明
图1显示根据本发明实施例的传感材料的制备方法流程图。
图2显示根据本发明实施例的传感系统。
图3a、3b为本发明实施例1及比较例2~4所制备的不同传感材料的X射线衍射光谱。
图4为本发明实施例6的拉曼光谱。
图5~10为本发明实施例7中根据本发明实施例的不同传感材料在不同参数条件下所得的傅立叶红外线(FT-IR)光谱。
图11~13为本发明比较例5在不同待测气体(PH3)浓度下所得的傅立叶红外线(FT-IR)光谱。
图14为本发明比较例6的傅立叶红外线(FT-IR)光谱。
【主要组件符号说明】
10、20、30、40、50、60~步骤;
18~待测气体缸;
28~干燥压缩空气缸:
38、38’~质量流量控制器;
48~化学滤网;
58~混合腔体;
68~测试腔体;
78~分析系统。
具体实施方式
以下特举出本发明的实施例,并配合附图作详细说明,而在附图或说明中所使用的相同符号表示相同或类似的部分,且在附图中,实施例的形状或厚度可扩大,并以简化或方便标示。另外,将分别描述说明附图中各组件的部分,值得注意的是,附图中未绘出或描述的组件,为所属技术领域的技术人员所知的形状。另外,特定的实施例仅为揭示本发明使用的特定方式,其并非用以限定本发明。
本发明提供一种传感材料的制备方法,其中传感材料为负载金属氧化物的二氧化钛纳米管(metal oxide loaded titanium dioxide(TiO2)nanotubes),而金属氧化物可包括CuO、AgO、Au2O3、Fe2O3或上述任意组合。本发明提供的传感材料用于侦测待测气体,其中待测气体可包括一含磷化合物、砷化氢(AsH3)、乙硼烷(B2H6)、邻苯二甲酸二(2-乙基己)酯(di(2-ethylhexyl)phthalate,DEHP)或上述任意组合。上述含磷化合物可包括磷化氢(PH3)、磷酸(H3PO4)、二甲基甲基磷酸酯(dimethylmethylphosphonate,DMMP)、亚磷酸三甲酯(trimethyl phosphate,TMB)、磷酸三甲酯(trimethyl phosphate,TMPO)或上述任意组合。在本发明实施例中,传感材料主要是以所负载的金属氧化物与待测气体反应的方式来实现传感。
图1显示根据本发明实施例的传感材料的制备方法流程图。首先进行步骤10,提供一金属氧化物前驱物(metal oxide precursor)的水溶液。在步骤10中,可依所需负载在二氧化钛纳米管的金属氧化物而选择合适的金属氧化物前驱物。举例来说,可使用Cu(NO3)2作为CuO的前驱物。或者,可使用AgNO3作为AgO的前驱物。又或者,可使用Fe(NO3)3作为Fe2O3的前驱物。或者,可使用HAuCl4作为AuO的前驱物。
接着进行步骤20,将二氧化钛纳米管或其水溶液与金属氧化物前驱物水溶液混合以形成一混合物,其中二氧化钛纳米管与金属氧化物前驱物的混合摩尔数比例约为10∶1至1∶1,在一些实施例中,可为4∶1。此外,在一些实施例中使用具有高比表面积(BET)的二氧化钛纳米管,例如比表面积约为200-400平方米/克(m2/g)的二氧化钛纳米管,以提高w金属氧化物的负载重量份,进而提高传感材料的灵敏度。二氧化钛纳米管的径长比可约为1∶35至1∶160,且其合成可使用二氧化钛结晶粉末为前驱物。在一实施例中,先将二氧化钛结晶粉末加入碱液中,再置入高温反应釜锻烧,接着进行酸洗及过滤,以完成二氧化钛纳米管的合成。应理解的是,上述合成二氧化钛纳米管的方式仅为举例,本发明可使用以各种方式合成或市售的二氧化钛纳米管。
接着进行步骤30,将一弱碱加入混合物中以调整混合物的pH值至约为中性,例如pH值约为6.5-7.5,或pH值约为7。弱碱可为各种有机或无机弱碱,例如Na2CO3、NH3、C6H5NH2、CH3NH2、CH3CH2NH2或上述任意组合。应注意的是,本发明实施例在步骤30是使用弱碱来调整混合物的pH值,可避免因强碱例如氢氧化钠(NaOH)造成混合物部分区域金属浓度过高产生聚集,而降低金属氧化物的负载量及分散度。
接着进行步骤40,将pH值调整至约为中性的混合物分散于水中并加热进行水热离子嵌入,使金属氧化物均匀分散并负载于二氧化钛纳米管表面。应注意的是,发明人发现步骤40中先进行水分散再进行水热离子嵌入,比起不进行水分散直接进行水热离子嵌入,也可提高所制备传感材料中金属氧化物的分散度。在一些实施例中,步骤40中的加热为在90-100℃下加热12-36小时或18-24小时。
在步骤40之后进行步骤50,过滤混合物以留下固体部分,固体部分为负载有金属氧化物及其前驱物的二氧化钛纳米管,其中部分金属氧化物前驱物已转变成氧化态,也就是金属氧化物。为使所有的金属氧化物前驱物可以完全氧化转变成金属氧化物,将固体部份置入一持续通氧的加热炉中锻烧,以形成负载一金属氧化物的二氧化钛纳米管,此时完成传感材料的制备。通氧的流量可为约5-10升/分钟,或为5-6升/分钟。在一些实施例中,可在锻烧固体部分时持续向加热炉中通入空气。在一些实施例中,锻烧固体部分为在250-350℃下锻烧约3-9小时,或为3-6小时。应注意的是,发明人发现在步骤50中,比起在不通氧锻烧的加热炉中锻烧固体部分,在持续通氧的加热炉中锻烧固体部份将可提高所制备传感材料中金属氧化物的分散度。
测量制备的传感材料的比表面积(BET),其大抵约为114-165m2/g,或为134-165m2/g。
在本发明的实施例中,所负载金属氧化物的金属元素相对于钛元素原子比例约为10-50%,或为20-40%。然而在其它实施例中可能更高或更低。
以下将叙述本发明实施例的传感方法。将待测气体由待测气体缸18经质量流量控制器38通入一混合腔体58,且将干燥压缩空气由干燥压缩空气缸28经化学滤网48及质量流量控制器38’通入混合腔体58,使待测气体及净化的干燥压缩空气充分混合,以下将称充分混合的待测气体及净化的干燥压缩空气为一混合气体。将传感材料设置于测试腔体68中,且使传感材料平铺盖满承载平台。将具有一特定待测气体浓度的混合气体以一流量从混合腔体58通入测试腔体68中,使混合气体可均匀贯穿传感材料。将一以光谱仪搭配可连续侦测的光学反射式套组的分析系统78连结至测试腔体68,其中分析系统78会在混合气体通入期间分析传感材料表面的光吸收特性。在一些实施例中,可使用拉曼光谱仪(Raman spectroscopy)系统搭配可连续侦测的光学反射式套组的分析系统。在其它实施例中,可使用傅立叶红外线光谱仪(Fourier transform infrared spectroscopy,FT-IR)系统搭配可连续侦测的光学反射式套组的分析系统。在一些实施例中,光学反射式套组可加热混合气体以缩短测试时间。通入测试腔体68的混合气体流量可约为1-30升/分钟,例如1升/分钟、15升/分钟或30升/分钟,而待测气体的浓度可约为1000ppb-100ppt,例如500ppb、200ppb、1ppb或500ppt。本发明所提供的传感材料对于待测气体具有高的拦截效率,例如高于98%的拦截效率,且可侦测到ppt等级的待测气体。应注意的是,本发明实施例所提供的传感方法的优点之一是可达到实时传感而不需要花费时间等待传感结果。
本发明所提供的传感材料(负载金属氧化物的二氧化钛纳米管)至少具有以下优点:(1)传感材料中所负载金属氧化物的分散度及负载重量高;(2)对于待测气体具有高捕集率;(3)可侦测达ppt等级的待测气体;(4)具有光谱传感特性。另外,本发明所提供的传感方法可实时侦测待测气体,并且可在较低温下(例如60℃)进行传感。
以下将叙述根据本发明所提供的传感材料的制备方法及传感方法的各实施例及比较例。
【传感材料的制备方法】
实施例1:负载氧化铜的二氧化钛纳米管
(1)取0.625克二氧化钛(Degussa P25)加入预先混合的2.5克NaOH及12.5毫升去离子水中,形成一混合物A。
(2)将步骤(1)的混合物A置入高温反应釜,在200℃锻烧24小时。
(3)在加热后的混合物A中加入1.3毫升70%HNO3及200毫升去离子水,搅拌24小时,并过滤两次。
(4)取0.625克以上述步骤(1)~(3)所制备的二氧化钛纳米管加入200克的水中形成混合物B,以及取0.156克的Cu(NO3)2粉末加入10克的水中形成水溶液C。
(5)混合上述混合物B与水溶液C以形成混合物D,并于40℃下搅拌混合物D三分钟。
(6)将1M的Na2CO3溶液加入搅拌后的混合物D调整其pH值至7.0。
(7)将步骤(6)中pH值约为中性的混合物D分散至100克的水中,并于100℃下加热24小时。
(8)过滤干燥步骤(7)中加热后的混合物D,以留下固体部分E。
(9)在持续通入流量为5升/分钟的空气的环境中锻烧固体部分E以形成负载氧化铜的二氧化钛纳米管,其中所通入的空气为先以化学滤网(chemical filters)过滤的干燥压缩空气(dry compressed air)。对于上述步骤(1)~(9)所制备的传感材料进行比表面积(BET)的测量,结果显示其比表面积约为165m2/g。以穿透式电子显微镜(transmission electronmicroscopy,TEM)搭配能量分散光谱仪(energydispersive x-ray spectroscopy,EDX)测量实施例1所制备传感材料中所负载氧化铜的铜元素负载重量,得到铜元素相对于钛元素的原子比例约为21%。
比较例1:负载氧化铜的二氧化钛纳米管
如实施例1所述的制备方法,其中将步骤(4)取0.156克的Cu(NO3)2粉末置换成0.031克的Cu(NO3)2粉末。以穿透式电子显微镜(TEM)搭配能量分散光谱仪(EDX)测量比较例1所制备传感材料中铜元素相对于钛元素的原子比例,结果约为5%。
比较例2:以强碱(NaOH)调整pH值
如实施例1所述的制备方法,其中将步骤(6)的1M的Na2CO3溶液置换成0.6M的NaOH溶液。
比较例3:未分散至100克水中
如实施例1所述的制备方法,其中省略步骤(7)的分散至100克的水中,而直接进行加热。
比较例4:在未通入空气的环境中锻烧固体部分E
如实施例1所述的制备方法,其中锻烧固体部分E时不通入空气。
比较例2~4所制备的传感材料中铜元素相对于钛元素的原子比例约为21%。
以X射线衍射(X-ray diffraction,XRD)分析依实施例1及比较例2~4所制备的传感材料的分散度,结果如图3a、3b所示。图3a中显示实施例1的传感材料的XRD光谱,而图3b中显示比较例2~4的传感材料的XRD光谱。如果所负载的氧化铜的分散度较好,铜的结晶度会较低,造成XRD光谱中较小的峰,然而如果分散度不佳,铜的结晶度会较高,造成XRD光谱中较大的峰。由图3a、3b可见实施例1的传感材料的铜信号的峰极小,表示所制备的传感材料所使用的条件可使其中负载的氧化铜具有良好的分散度,而比较例2(强碱滴定)、比较例3(未进行水分散)、比较例4(未通空气)的传感材料的铜信号的峰明显比实施例1大,表示氧化铜分散度较差。
实施例2:负载氧化银的二氧化钛纳米管
如实施例1所述的制备方法,其中将步骤(4)中取0.156克的Cu(NO3)2粉末加入10克的水中改为取0.156克的AgNO3粉末加入10克的水中以制备传感材料。
对所制备的传感材料进行比表面积(BET)的测量,结果显示其比表面积约为110-160m2/g。以穿透式电子显微镜(TEM)搭配能量分散光谱仪(EDX)测量实施例2所制备传感材料中所负载氧化银的银元素负载重量,得到银元素相对于钛元素的原子比例约为23.2%。
实施例3:负载氧化铁(Fe2O3)的二氧化钛纳米管
如实施例1所述的制备方法,其中将步骤(4)中取0.156克的Cu(NO3)2粉末加入10克的水中改为取0.156克的Fe(NO3)3粉末加入10克的水中以制备传感材料。
对所制备的传感材料进行比表面积(BET)的测量,结果显示其比表面积约为105-165m2/g。以穿透式电子显微镜(TEM)搭配能量分散光谱仪(EDX)测量实施例3所制备传感材料中所负载氧化铁的铁元素负载重量,得到铁元素相对于钛元素的原子比例约为16.3%。
实施例4:负载氧化铜(CuO)及氧化铁(Fe2O3)的二氧化钛纳米管
如实施例1所述的制备方法,其中将步骤(4)中取0.156克的Cu(NO3)2粉末加入10克的水中改为取0.140克的Cu(NO3)2粉末和0.0156克的Fe(NO3)3粉末加入10克的水中以制备传感材料。
对所制备的传感材料进行比表面积(BET)的测量,结果显示其比表面积约为105-165m2/g。以穿透式电子显微镜(TEM)搭配能量分散光谱仪(EDX)测量实施例4所制备传感材料中所负载氧化铜的铜元素及氧化铁的铁元素负载重量,得到铜元素及铁元素相对于钛元素的原子比例分别约为19%及1.5%。
实施例5:负载氧化金(AuO)的二氧化钛纳米管
如实施例1所述的制备方法,其中将金属前驱物替换成HAuCl4以制备传感材料。
对所制备的传感材料进行比表面积(BET)的测量,结果显示其比表面积约为105-165m2/g。以穿透式电子显微镜(TEM)搭配能量分散光谱仪(EDX)测量实施例5所制备传感材料中所负载氧化金的金元素负载重量,得到金元素相对于钛元素的原子比例约为11.6%。
【待测气体的传感方法】
提供如图2所示的传感系统,将待测气体由待测气体缸18经质量流量控制器38通入一混合腔体58,且将干燥压缩空气由干燥压缩空气缸28经化学滤网48及质量流量控制器38’通入混合腔体58,使待测气体及净化的干燥压缩空气充分混合形成一混合气体。将本发明实施例及/或比较例所制备的传感材料设置于测试腔体68中,且使传感材料平铺盖满承载平台。将具有一特定待测气体浓度的混合气体以一流量从混合腔体58通入测试腔体68中,使混合气体可均匀贯穿传感材料。使用一以光谱仪搭配可连续侦测的光学反射式套组的分析系统以分析混合气体通入期间传感材料表面的光吸收特性。
为确保本发明实施例所提供传感材料对于待测气体有高的拦截效率,将一Drager气体侦测器(Drager sensor hydrude)连接至测试腔体。在设置有实施例1的传感材料的测试腔体中通入流速为1升/分钟的混合气体,其中待测气体(在此为PH3)浓度为500ppb,并以Drager气体侦测器侦测由测试腔体通出的后端气体中待测气体的浓度,结果低于Dragon气体侦测器所能侦测到的下限(10ppb),由此证明本发明实施例所提供传感材料对于待测气体具有高于98%的拦截效率。
实施例6
在实施例6中,使用实施例2所制备的传感材料,及以磷化氢为待测气体,其中混合气体流量为1升/分钟,磷化氢浓度为500ppb,并使用拉曼光谱仪(Raman spectroscopy)搭配一光学反射式套组在通入混合气体期间分析传感材料表面的光吸收特性。在本实施例中,若通入测试腔体的磷化氢与传感材料反应形成P-O键结,P-O键结可被拉曼光谱仪侦测到。图4显示所得的拉曼光谱图,由图4可知在波长956±2cm-1有显著的特征峰,此特征峰可作为含磷化合物(如PH3)的定性与定量。
实施例7
同实施例6,但以傅立叶红外线光谱仪系统(FTIR)替换拉曼光谱仪。本实施例在不同的参数条件下测量FTIR光谱。表2显示所使用不同的参数条件,而图5~10显示所得的光谱,其特征峰明确易于分析判断。因此,本实施例可测得浓度在ppt等级的磷化氢气体。
表2
比较例5
同实施例7,但连续20或24小时通入混合气体于混合腔体中进行传感,并在特定时间点量测传感材料的FTIR光谱。表3显示使用的不同参数条件,而图11~13显示所得的光谱,由这些随时间变化的FTIR光谱可知,在900~1200cm-1之间的吸收强度有显著的变化。表4更显示图13所示光谱的信噪比(signal-to-noise ratio,S/N),由持续增加的信噪比可知传感材料持续地吸收待测气体。
表3
表4
比较例6
同比较例5,但将传感材料置换成比较例1制备的传感材料、将连续通入混合气体的时间改为连续4小时、并将待测气体(PH3)的浓度改为100ppb。所得FTIR光谱如图14所示。在连续通入混合气体4个小时后,相对于可测得ppt等级浓度待测气体的比较例5,比较例6甚至连100ppb浓度的待测气体都无法测得(S/N<1)。由此证明本发明所制备出具有较高的CuO负载度(铜元素相对于钛元素的原子比例约为21%)的传感材料为可侦测至ppt等级浓度待测气体的因素之一。
综上所述,本发明所提供的传感材料可使所负载的金属氧化物具有高负载重量及高分散度,而传感材料对待测气体更有高的捕集率,更重要的是,传感材料可侦测至ppt等级浓度的待测气体。另外,本发明所提供运用上述传感材料的传感方法可达到实时侦测待测气体。因此本发明可克服背景技术中无法侦测至ppt等级及无法实时侦测等问题。
本发明虽由以上较佳实施例揭露,然而其并非用以限定本发明的范围,任何所属技术领域的技术人员,在不脱离本发明的主题和范围内,当可做任意的改动与修饰,因此本发明的保护范围应当以权利要求所界定的范围为准。
Claims (16)
1.一种传感材料的制备方法,包括以下步骤:
a)提供一金属氧化物前驱物的水溶液;
b)混合二氧化钛纳米管与该金属氧化物前驱物的水溶液以形成一混合物;
c)以一弱碱调整该混合物的pH值至中性;
d)将该混合物分散于水中并加热;及
e)过滤该混合物以留下固体部分,并在持续通氧的环境中锻烧该固体部分,以形成负载一金属氧化物的二氧化钛纳米管。
2.根据权利要求1所述的传感材料的制备方法,其中该金属氧化物前驱物包括Cu(NO3)2、HAuCl4、AgNO3、Fe(NO3)3或上述任意组合。
3.根据权利要求1所述的传感材料的制备方法,其中该金属氧化物为CuO、AgO、Au2O3、Fe2O3或上述任意组合。
4.根据权利要求1所述的传感材料的制备方法,其中该二氧化钛纳米管与该金属氧化物前驱物的混合摩尔数比例约为10∶1至1∶1。
5.根据权利要求1所述的传感材料的制备方法,其中该弱碱包括Na2CO3、NH3、C6H5NH2、CH3NH2、CH3CH2NH2或上述任意组合。
6.根据权利要求1所述的传感材料的制备方法,其中步骤d)是在90-100℃下加热12-36小时。
7.根据权利要求1所述的传感材料的制备方法,其中步骤e)包括通入空气。
8.根据权利要求1所述的传感材料的制备方法,其中步骤e)是在250-350℃下锻烧约3-9小时。
9.一种传感材料,包括:
二氧化钛纳米管;及
金属氧化物均匀分散且负载于该二氧化钛纳米管上,其中该负载金属氧化物的二氧化钛纳米管的比表面积约为200-400平方米/克,且该金属氧化物的金属元素相对于钛元素的原子比例约为10-50%。
10.根据权利要求9所述的传感材料,该金属氧化物为CuO、AgO、Au2O3、Fe2O3或上述任意组合。
11.一种实时传感方法,包括:
提供如权利要求10所述的传感材料;
导入一待测气体与该传感材料反应;及
以拉曼光谱仪系统或傅立叶红外线光谱仪系统分析反应结果。
12.根据权利要求11所述的实时传感方法,该待测气体的浓度约为1000ppb-100ppt。
13.根据权利要求11所述的实时传感方法,该待测气体的流量约为1-30升/分钟。
14.根据权利要求11所述的实时传感方法,该传感方法用以传感该待测气体内的一含磷化合物,包括磷化氢、磷酸、二甲基甲基磷酸酯、亚磷酸三甲酯、磷酸三甲酯或上述任意组合。
15.根据权利要求11所述的实时传感方法,该传感方法用以检测该待测气体内的砷化氢AsH3、乙硼烷B2H6、邻苯二甲酸二(2-乙基己)酯或上述任意组合。
16.根据权利要求11所述的实时传感方法,还包括将一具加热功能的光学反射式套件与拉曼光谱仪系统或傅立叶红外线光谱仪系统连结。
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