201043574 六、發明說明： 【發明所屬之技術領域】 本發明是有關於一種氧化物，特別是指-種由多元高 熵合金構成的合金氧化物光電半導體及其製作方法。 【先前技術】 傳統上，合金的概念是以一種原子百分比超過編％ 的金屬元料主，並添加不同的元素而成的混合物，例如 铭合金，咼熵合金（High-Entrcmv ΑΠ 、 Ο201043574 VI. Description of the Invention: [Technical Field] The present invention relates to an oxide, and more particularly to an alloy oxide optoelectronic semiconductor composed of a multi-element high-entropy alloy and a method of fabricating the same. [Prior Art] Conventionally, the concept of an alloy is a mixture of a metal atomic percentage exceeding a gram% of a metal element and adding different elements, such as an alloy of the name, a enthalpy entropy alloy (High-Entrcmv ΑΠ, Ο
g tntr〇py A„〇ys)則迥異於傳統的 &金概念，是由多種主尊开丰 p. ^ , 要兀素、且其中每個主要元素都具 有局的原子百分比，但不超過35at%所成的混合物，—般 為了與傳統合金有明顯的區隔，且充分發揮多元素高^ 的效應，-般定義高熵合金的主要元素數目不小於 ： 是多元高熵合金。 y 南嫡合金因為各組成元素皆是主要元素，以目前已知 元素的組成而言’彳開發的合金系統無以計數，也因此數 1、種類過於龐大’針對高熵合金的研究往往局部且片 斷’但累積至今，多元高熵合金由於高熵效應促進各主要 元素的均句混合’因此在晶體結構上會呈現容易形成體心 立方（BCC )、面心立方（FCC )結晶，4為非晶質 (amorphous)等結構，並在材料性質方面，呈現具有高硬 度、耐高溫軟化、耐高溫氧化、耐腐蝕等特性，此外，多 元高熵合金的微結構因為多個元素的擴散與重分配而傾= 奈米化，對於快速凝固或真空鍍膜過程而言，更展現非晶 化傾向，因此在材料應用上具有很大的產業潛力。 3 201043574 ® ’光電元件例如平面顯示器(咖)、太陽能電 L、/r ’、觸控式面板螢幕、電子書(“叫等的構 ^彳動等均與光脫離不了關係，因此，其 於關鍵材料本身的# 士从/ 如展曰園 :特性與對光”透度，而受龍制；㈣是例如目= 电^件中作為電極之料透”電材料，僅有ITQ、Zn〇和 岭等η型的透明導電氧化物，以及p型的—、 ⑽'、⑽6〇2和抓2〇2等數量有限的幾種可供選擇應 用’更是目前光電技術發展的技術瓶頸之_。 " 因此，若能以多元高熵合金的優異材 礎’開發具有光電半導體特性的新材料，將能促使 術往前邁進一大步。 【發明内容】 曰由於目W亚未有以高滴合金開發具有光電特性，特別 是透明導電材料、透明絕緣材料的相關研究，合金 :為各組成元素皆是主要元素’卩目前已知元素的組成而 ^可開發的合金系統將無以計數，因此在毫無開發基礎 的前提下，發明人自-般「鐘膜」均須具備的高硬度1 刮钱作發想，而敎常見於_之組份、且本身即呈有古 硬度特徵的鈦（Ti)、銳（v)、路（c〇、錯O': (Ta)為主要元素成高熵合金，並與氧、或是氮、氧結合 成合金氧化物進行研究。 發明人根據理論推算，當氧的原子百分比在佔合金氧 化物的33.0㈣〜6G.GGat%，且多元高熵合金的每—元素的 201043574 原子百分比佔合金氧化物的3.00at% 〜18〇〇at%時，結合所 成的合金氧化物應俱備有適用於光電元件的例如透明、絕 緣體、半導體等特性，而此些特性與其中氧所占原子百分 二關，且同時因為氧的束缚能高，所以其中有些特性不 -定能於實驗中被驗證出來’但是如果再利用添加氮，添 加原子百分比在H.00at%〜33.00at%，緩和氧的高束缚能的 特性，則有較大的希望能在預定原子百分比的範圍下得到 具有例如絕緣特性、半導體特性，或是透明度高的合 化物以供光電技術領域應用。 再經過實驗發現，當氧的原子百分比大於％義作 所成的合金氧化物具有透明且絕緣的特性；而當氧的原子 。百分比是21.9at%〜伽at% ’且氮的原子百分比是 ^2.5at%時’所成的合金氧化物則具有光電半導體的特 Ο f發明之功效在於··提供—種新的、由鈦、鈒、路、 :::構成的多元高燏合金與氧或氮、氧所成 電二::舰金氧化物分別具有透明絕緣體特性與； "知f生’緹供目前光電技術領域中多樣具有光恭 =:Γ 一一發展。 有關本么明之别逑及其他技術内容點 以下配合參考圖式之二個〃 刀政在 清楚的呈現。 4α例的詳細說明中，將可 么明人m0.2v02Cr〇2Zr〇2Ta。“巴材，配合基礎真空 201043574 (Base pressure ) 3·0χ l0-6T〇rr、工作壓力（w〇rking pressure) 3.〇x1〇-3Tcm、射頻功率（DC p〇wer) 2〇〇w，並 分別在氧氣/氧氣+氬氣的通入氣氛比（〇2/〇2+Ar rati〇)是 is% 、氧氣/氧氣+氮氣+氩氣的通入氣氛比（〇2/〇2+N2+Ar r_)是2.0%，以及氮氣/氧氣+氮氣+氮氣的通入氣氛比 (N2/02+N2+Ar ratio)是50%，以乾材與基材間距7〇顏 濺鍍（sputtering)沉積20分鐘，分別於玻璃基材上得到 C Ti3'77Vl7’85C^7'36Zl-5.47Ta7 〇3 ) 41 48〇5 8 52 (以下簡稱第一合 金氧化物）、（Ti3.58V8.62Cri〇 8办 5山9 2。）％ a μ%μ (以下簡稱第二合金氧化物）。 麥閱圖1 ’圖1是第一、二合金氧化物的x_ray繞射 圖’由圖中結果可驗證第一、二合金氧化物均是非晶態結 構。 參閱圖2至圖7 ’圖2至7分別是以鈦、釩、锆、组、 鉻及氧的第一、一合金氧化#勿x_ray光電能譜圖（ P^t〇electronic spectr〇sc〇py) ’綜合圖2至圖6可以驗證隨 著氮原子的加人，第：合金氧化物的束缚能減少，亦即， 價電子被增加或氧化態減少，也就是說合金氧化物會因氮 原子的加人而光學能隙減少，導電性漸增；換句話說，本 發明合金氧化物確實可藉由調整氮原子的加入而呈現半導 體特性。另，由圖7可知，氧原子束缚能並未受到說原子 的加入而改變其大小；肖句話說，氮原子的加入對於高熵 合金原子影響較大。 參閱圖8,圖8是第一、二合金氧化物分別在厚度是 201043574 290nm及326nm時對光波長為2〇〇_1〇〇〇nm的穿透率表現， 由量測結果可以知道，第一合金氧化物薄膜對可見光(且约 观的穿透率’主因是其光學能隙較大··而第二合金氧化物 則由於有氮的加入.，而呈現對可見光具有約2〇%光穿透率 的光電半導體特性。 參閱圖9、圖10’圖9、圖1〇分別是第一、二合金氧 化物非直接能隙圖譜，由1中 阳Z、甲异可以得知第一合金氧化 物的非直接能隙較大，為 Ο ❹ 易2.38ev，而第二合金氧化物則因 為氮的加人呈現半導體特性，㈣接能隙減少為195ev。 再將第一、二合金氧化物的材料電性整理如下表，可 更進一步地驗證本發明由炙 丄 的材料特性表1。g tntr〇py A„〇ys) is different from the traditional & golden concept, which is composed of a variety of main cults p. ^ , 兀 、 , and each of the main elements has a local atomic percentage, but not more than The mixture of 35at% is generally distinguished from the traditional alloy, and the effect of multi-element high ^ is fully exerted. The number of main elements of the high-entropy alloy is generally defined as: multi-element high-entropy alloy. Niobium alloys are the main elements because of the composition of the elements. In terms of the composition of the currently known elements, the alloy system developed by 彳 is not counted, so the number 1 and the type are too large. The research on high-entropy alloys is often partial and fragmented. However, until now, multi-enriched high-entropy alloys promote the homogenous mixing of the main elements due to the high entropy effect. Therefore, it is easy to form body-centered cubic (BCC), face-centered cubic (FCC) crystals, and amorphous in the crystal structure. (amorphous) and other structures, and in terms of material properties, exhibits high hardness, high temperature softening resistance, high temperature oxidation resistance, corrosion resistance, etc. In addition, the microstructure of the multi-element high-entropy alloy is due to multiple elements. Diffusion and redistribution and tilting = nanocrystallization, which has a tendency to amorphize for rapid solidification or vacuum coating processes, and therefore has great industrial potential in material applications. 3 201043574 ® 'Photoelectric components such as flat panel displays ( Coffee), solar power L, /r ', touch panel screen, e-book ("calling and other structures, etc." are not related to light, therefore, its key material itself #士从/如展Gion: the characteristics and the light penetration, and the dragon system; (4) is, for example, the material as the electrode in the electric material, the electrical material, only the IRQ, such as ITQ, Zn and ridge, transparent conductive oxide And p-type -, (10)', (10)6〇2 and grab 2〇2 and a limited number of alternative applications are more technical bottlenecks in the development of optoelectronic technology. The excellent material foundation of entropy alloys' development of new materials with photo-semiconductor properties will enable the advancement of the process to a large step. [Summary] 曰Because the development of high-drop alloys has no photoelectric properties, especially transparent Conductive material, transparent insulating material Related research, alloy: for each component is the main element '卩 The composition of the currently known elements and ^ can be developed alloy system will not count, so in the absence of development basis, the inventor from the general "clock The film must have the high hardness of 1 scraping for the sake of thinking, while the bismuth is common in the composition of _, and itself has the characteristics of ancient hardness of Ti (Ti), sharp (v), road (c〇, wrong O ': (Ta) is the main element into a high-entropy alloy, and is combined with oxygen, or nitrogen, oxygen to form an alloy oxide. The inventor calculated according to the theory, when the atomic percentage of oxygen is 33.0 (four) of the alloy oxide ~ 6G.GGat%, and the 201043574 atomic percentage of each element of the multi-element high-entropy alloy accounts for 3.00at%~18〇〇at% of the alloy oxide, and the alloy oxide formed should be suitable for photovoltaic elements. Such as transparency, insulators, semiconductors and other characteristics, and these characteristics are related to the atomic percentage of oxygen, and at the same time because of the high binding energy of oxygen, some of the characteristics are not - can be verified in the experiment 'but if Reuse nitrogen to add atoms When the ratio is in H.00at%~33.00at%, the characteristics of the high binding energy of oxygen are alleviated, and there is a large expectation that a property such as insulating property, semiconductor property, or transparency can be obtained in a predetermined atomic percentage range. The compound is used in the field of optoelectronic technology. It has been found through experiments that when the atomic percentage of oxygen is greater than the %, the alloy oxide has a transparent and insulating property; and when the oxygen is atomic. The percentage is 21.9 at% to gamat%% 'and the atomic percentage of nitrogen is ^2.5 at%'. The alloy oxide formed has the characteristics of an optoelectronic semiconductor. The effect of the invention lies in the provision of a new type of titanium. , 鈒, 路, ::: constitutes a multi-component sorghum alloy with oxygen or nitrogen, oxygen into electricity two:: ship gold oxide has a transparent insulator characteristics and; " know fsheng '缇 for the current field of optoelectronic technology Diverse and radiant =: Γ One-on-one development. The details of this and other technical content points are clearly presented below with reference to the two drawings. In the detailed description of the 4α example, it is possible to m0.2v02Cr〇2Zr〇2Ta. "Bamu, with foundation vacuum 201043574 (Base pressure) 3·0χ l0-6T〇rr, working pressure (w〇rking pressure) 3.〇x1〇-3Tcm, RF power (DC p〇wer) 2〇〇w, And in the oxygen/oxygen + argon atmosphere ratio (〇2/〇2+Ar rati〇) is the ratio of the inlet atmosphere of is%, oxygen/oxygen+nitrogen+argon (〇2/〇2+N2) +Ar r_) is 2.0%, and the ratio of nitrogen/oxygen + nitrogen + nitrogen to the atmosphere (N2/02 + N2 + Ar ratio) is 50%, and the distance between the dry material and the substrate is 7 〇 sputtering. Deposited for 20 minutes, respectively, on the glass substrate to obtain C Ti3'77Vl7'85C^7'36Zl-5.47Ta7 〇3) 41 48〇5 8 52 (hereinafter referred to as the first alloy oxide), (Ti3.58V8.62Cri〇 8 do 5 mountain 9 2))% a μ%μ (hereinafter referred to as the second alloy oxide). Wheat Figure 1 'Figure 1 is the first and second alloy oxide x_ray diffraction pattern' can be verified by the results The first and second alloy oxides are all amorphous. Refer to Figure 2 to Figure 7 'Figures 2 to 7 are the first and first alloys of titanium, vanadium, zirconium, group, chromium and oxygen. #勿x_ray Photoelectric Energy Spectrum (P^t〇electronic spectr Sc〇py) 'Comprehensive Figure 2 to Figure 6 can verify that as the nitrogen atom is added, the binding energy of the alloy oxide is reduced, that is, the valence electron is increased or the oxidation state is reduced, that is, the alloy oxide will The optical energy gap is reduced due to the addition of nitrogen atoms, and the conductivity is gradually increased; in other words, the alloy oxide of the present invention can exhibit semiconductor characteristics by adjusting the addition of nitrogen atoms. Further, as shown in Fig. 7, oxygen atom binding It can be changed without changing the size of the atom; in other words, the addition of nitrogen atoms has a greater influence on the high-entropy alloy atoms. Referring to Figure 8, Figure 8 shows that the first and second alloy oxides are respectively at a thickness of 201043574 290nm. And at 326nm, the transmittance of light at a wavelength of 2〇〇_1〇〇〇nm is obtained. From the measurement results, it can be known that the first alloy oxide film is visible light (and the apparent transmittance is mainly due to its optics). The energy gap is large. The second alloy oxide exhibits photo-semiconductor characteristics of about 2% by transmittance of visible light due to the addition of nitrogen. See Figure 9, Figure 10, Figure 9, Figure 1. 〇 are the first and second alloy oxygen The non-direct energy gap map of the compound, from 1 yang, Z, can be known that the first alloy oxide has a large indirect energy gap, which is Ο 2.3 2.38 ev, while the second alloy oxide is added by nitrogen. The semiconductor characteristics are exhibited, and (4) the junction gap is reduced to 195 ev. The materials of the first and second alloy oxides are electrically organized as follows, and the material properties of the invention according to Table 1 can be further verified.
N :咖如 ^ ： Hall coefficient β ·' Hall mobility . 焉熵合金構成的合金氧化物 β σ ) (cm2/VS ) ((Ω cm)"1 ) — 一 0.017 2.75xl〇-2N : Cafe as ^ : Hall coefficient β · ' Hall mobility . Alloy oxide composed of 焉 entropy alloy β σ ) (cm2/VS ) ((Ω cm)"1 ) — A 0.017 2.75xl〇-2
Rh σ · electrical conductivity ^此外發明人亦以相同之_法，㈣另二組高摘合金 !!；b!,(Ti6-64V-6C^^ n14,c. ϋ32.5 (以下簡稱第四合金氡化物 > 其中，氮的原子百 刀比/刀別佔I4.2at%及32 5at«/ s , ^ · aU ，目的是進一步驗證氮含量 的改艾對於光電性質的影響。Rh σ · electrical conductivity ^ In addition, the inventor also uses the same method, (4) the other two groups of high-stretched alloys!!;b!,(Ti6-64V-6C^^ n14,c. ϋ32.5 (hereinafter referred to as the fourth alloy) Telluride > Among them, the atomic ratio of nitrogen to the knife is 11.2at% and 32 5at«/ s , ^ · aU , the purpose is to further verify the effect of the nitrogen content on the photoelectric properties.
參閱圖11、圖12，圖u、R u 間11圖12分別是第三、四合金 乳化物非直接能隙圖譜，由 虫其中叶鼻可以得知第三合金氧 201043574 類似地，第三、四合金氧化物的材料性質整理如下 二’由表中各數據分析可知，氮含量增加造成非直接能隙 減厂而導電性值增加，亦可驗證第―、二合金氧化物的 材科特性如之前所述，因為束縛能減少，料，價電子被 增加，或氧化態減少而確實具有光電半導體性質。Referring to Figure 11, Figure 12, Figure u, R u between 11 and Figure 12 are the third and fourth alloy emulsion indirect energy gap map, the third alloy oxygen can be known from the insect leaf nose 201043574 Similarly, third, The material properties of the four alloy oxides are as follows: 'As can be seen from the analysis of the data in the table, the increase in nitrogen content causes the indirect energy gap to decrease in the factory and the conductivity value increases, and the material properties of the first and second alloy oxides can also be verified. As described earlier, since the binding energy is reduced, the valence electrons are increased, or the oxidation state is reduced to have an optoelectronic semiconductor property.
carrier density Rh ： Hall coefficient · Ability σ ： electrical conductivityCarrier density Rh : Hall coefficient · Ability σ : electrical conductivity
人入综上所述，本發明主要是提供一種新的、由多元高 合金構成的合金氧化物及其製作方法，確實可以原子百 比疋3.〇〇at% 〜18 〇〇at%的範圍下以鈦、釩、鉻、錘、钽 成多'元高熵合金後，再分別調整氧、氮與多元高熵合金 ^份關係’而得到分別具有透明且絕緣特性，以及光電 導體特性的合金氧化物，除了可以豐富目前的高燏合金 匕物的系統之外，還可以供光電元件應用而大幅促進光 元件的技術發展，確實達到本發明之目的。 准以上所述者，僅為本發明之較佳實施例而已，當不 月匕以此限定本發明實施之範圍，即大凡依本發明申請專利 祀圍及發明說明内容所作之簡單的等效變化與修_，皆仍 屬本發明專利涵蓋之範圍内。 8 201043574 【圖式簡單說明】 圖1是一 X-ray繞射圖，說明本發明之實驗所製作的第 一、二合金氧化物是非晶態結構； 圖2是一光電能譜圖，說明本發明之實驗所製作的第 一、二合金氧化物的鈦元素束缚能關係； 圖3是一光電能譜圖，說明本發明之實驗所製作的第 一、二合金氧化物的飢元素束缚能關係； 圖4是一光電能譜圖，說明本發明之實驗所製作的第 〇 一、二合金氧化物的锆元素束缚能關係； 圖5是一光電能譜圖，說明本發明之實驗所製作的第 一、二合金氧化物的钽元素束缚能關係； 圖6是一光電能譜圖，說明本發明之實驗所製作的第 一、二合金氧化物的鉻元素束缚能關係； 圖7是一光電能譜圖，說明本發明之實驗所製作的第 一、二合金氧化物的氧元素束缚能關係； 圖8是一光穿透率曲線圖，說明驗證本發明之實驗所 ^ 製作的第一、二合金氧化物對光波長為200-1 OOOnm的光穿 透率； 圖9是一非直接能隙圖，說明本發明之實驗所製作的 第一合金氧化物的非直接能隙； 圖10是一非直接能隙圖，說明本發明之實驗所製作的 第二合金氧化物的非直接能隙； 圖11是一非直接能隙圖，說明本發明之實驗所製作的 一第三合金氧化物的非直接能隙；及 201043574 圖12是一非直接能隙圖，說明本發明之實驗所製作的 一第四合金氧化物的非直接能隙。In summary, the present invention mainly provides a new alloy oxide composed of a multi-element high-alloy and a manufacturing method thereof, which can be truly in the range of 原子%% 1818% 18at% After titanium, vanadium, chromium, hammer, and bismuth are formed into a multi-element high-entropy alloy, the relationship between oxygen, nitrogen and multi-equivalent high-entropy alloys is adjusted separately to obtain alloys having transparent and insulating properties and photoconductor properties. Oxides, in addition to systems that can enrich the current sorghum alloys, can also be used for optoelectronic component applications to greatly promote the technical development of optical components, and indeed achieve the object of the present invention. The above is only the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, that is, the simple equivalent change of the patent application and the description of the invention. And repairs, are still within the scope of the invention patent. 8 201043574 [Simplified description of the drawings] Fig. 1 is an X-ray diffraction diagram illustrating that the first and second alloy oxides produced by the experiment of the present invention are amorphous; FIG. 2 is a photoelectric energy spectrum, illustrating The titanium element binding energy relationship of the first and second alloy oxides produced by the experimental experiment; FIG. 3 is a photoelectric energy spectrum diagram illustrating the hungry element binding energy relationship of the first and second alloy oxides produced by the experiment of the present invention Figure 4 is a photoelectric energy spectrum illustrating the zirconium binding energy relationship of the first and second alloy oxides produced by the experiment of the present invention; Figure 5 is a photoelectric energy spectrum illustrating the experiment made by the experiment of the present invention; The bismuth element binding energy relationship of the first and second alloy oxides; Fig. 6 is a photoelectric energy spectrum diagram illustrating the chromium element binding energy relationship of the first and second alloy oxides produced by the experiment of the present invention; Fig. 7 is a photoelectric An energy spectrum diagram illustrating the oxygen element binding energy relationship of the first and second alloy oxides produced by the experiment of the present invention; FIG. 8 is a light transmittance curve diagram illustrating the first experiment performed by the experimental body of the present invention. Dioxide oxide The light transmittance is 200-1 OOOnm; FIG. 9 is an indirect energy gap diagram illustrating the indirect energy gap of the first alloy oxide produced by the experiment of the present invention; FIG. 10 is an indirect energy gap. Figure shows the indirect energy gap of the second alloy oxide produced by the experiment of the present invention; Figure 11 is a non-direct energy gap diagram illustrating the indirect energy gap of a third alloy oxide produced by the experiment of the present invention. And 201043574 FIG. 12 is an indirect energy gap diagram illustrating the indirect energy gap of a fourth alloy oxide produced by the experiment of the present invention.
10 201043574 【主要元件符號說明】 益 I > »\ Ο10 201043574 [Description of main component symbols] Benefit I > »\ Ο
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