TWI579393B - Oxide-type semiconductor material and sputtering target - Google Patents

Oxide-type semiconductor material and sputtering target Download PDF

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TWI579393B
TWI579393B TW101115746A TW101115746A TWI579393B TW I579393 B TWI579393 B TW I579393B TW 101115746 A TW101115746 A TW 101115746A TW 101115746 A TW101115746 A TW 101115746A TW I579393 B TWI579393 B TW I579393B
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oxide
semiconductor material
tft
type semiconductor
atoms
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TW201303049A (en
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德地成紀
石井林太郎
附田龍馬
久保田高史
高橋廣己
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三井金屬鑛業股份有限公司
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Description

氧化物型半導體材料及濺鍍靶 Oxide semiconductor materials and sputtering targets

本發明係關於一種供以形成構成液晶顯示器(display)等顯示裝置之半導體元件的半導體材料，尤其係關於一種含有鋅(Zn)氧化物與錫(Sn)氧化物，且含有鋯(Zr)以作為摻雜物(dopant)的氧化物型半導體材料。 The present invention relates to a semiconductor material for forming a semiconductor element constituting a display device such as a liquid crystal display, and more particularly to a zinc (Zn) oxide and a tin (Sn) oxide, and containing zirconium (Zr) An oxide type semiconductor material as a dopant.

近年來，由液晶顯示器所代表之薄型電視等之顯示裝置，生產量的增加、與大畫面化的傾向很顯著。而且，就該顯示裝置而言，使用薄膜電晶體(Thin Film Transistor，簡稱TFT)作為開關(switching)元件的主動陣列型(active matrix type)的液晶顯示器廣為普及。 In recent years, display devices such as thin televisions represented by liquid crystal displays have a tendency to increase in throughput and increase in size. Further, in the display device, an active matrix type liquid crystal display using a thin film transistor (TFT) as a switching element is widely spread.

在以如前述之TFT作為開關元件的顯示裝置中，係使用氧化物型半導體材料作為TFT的構成材料。就該氧化物型半導體材料而言，有一種屬於透明氧化物半導體材料之一的IGZO(In-Ga-Zn-O系氧化物)受到矚目(參照專利文獻1)。由於該IGZO的載子(carrier)遷移率僅次於目前所使用之多晶矽，且如非晶矽(amorphous silicon,a-Si)TFT特性的特性差異小，因此作為今後的半導體材料為有希望的材料而漸開始廣受利用。 In a display device using a TFT as the switching element as described above, an oxide semiconductor material is used as a constituent material of the TFT. In the oxide-type semiconductor material, IGZO (In-Ga-Zn-O-based oxide), which is one of the transparent oxide semiconductor materials, has attracted attention (see Patent Document 1). Since the carrier mobility of the IGZO is second only to the polysilicon currently used, and the difference in characteristics of amorphous silicon (a-Si) TFT characteristics is small, it is promising as a semiconductor material in the future. The materials are gradually becoming widely used.

然而，在薄型電視等之液晶顯示器中，出現了顯示方式的改變。具體而言係除平面顯示(2D)外，且提供有能夠立體顯示(3D)的液晶顯示器。在該立體顯示(3D)型的液晶顯示器中，係以藉由利用切換液晶之控制而使顯示畫面的 左右呈現相異影像之方式而予以實現。因此，為了如前述之立體顯示型的液晶顯示器，期盼可實現更高速之響應速度的開關元件。 However, in a liquid crystal display such as a thin television, a change in display mode has occurred. Specifically, in addition to the flat display (2D), a liquid crystal display capable of stereoscopic display (3D) is provided. In the stereoscopic display (3D) type liquid crystal display, the display screen is made by controlling by switching the liquid crystal This is achieved by presenting different images to the left and right. Therefore, in order to the liquid crystal display of the stereoscopic display type as described above, a switching element which can realize a higher speed response speed is desired.

為了對應於如前述之液晶顯示器之顯示方式的改變，已進行種種如IGZO之類的氧化物型半導體材料的開發。成為該高速之響應速度的TFT，高載子遷移率則為重要。例如，在IGZO中，相較於a-Si IGZO的載子遷移率係大於1至2位數，為在5至10cm2/Vs左右。因此，如果是該IGZO係為能夠使用作為屬於立體顯示型液晶顯示器之開關元件的TFT之構成材料，故為了實現更高規格的液晶顯示器，殷切盼望可實現進一步高速之響應速度的TFT之構成材料。 In order to cope with a change in the display mode of the liquid crystal display as described above, development of various oxide type semiconductor materials such as IGZO has been carried out. As the TFT of this high-speed response speed, high carrier mobility is important. For example, in IGZO, the carrier mobility compared to a-Si IGZO is greater than 1 to 2 digits, and is about 5 to 10 cm 2 /Vs. Therefore, if the IGZO is a constituent material of a TFT which is a switching element of a stereoscopic display type liquid crystal display, in order to realize a liquid crystal display of a higher specification, it is eager to realize a constituent material of a TFT having a higher speed response speed. .

此外，該IGZO係因在形成TFT時必須進行350℃以上之退火(anneal)處理，故有人指出難以利用於如利用可撓性(flexible)基板等之有機EL面板及電子紙張之類的無法進行高溫熱處理之顯示裝置的問題點。 In addition, the IGZO is required to be subjected to an annealing treatment at 350 ° C or higher when forming a TFT. Therefore, it has been pointed out that it is difficult to use it such as an organic EL panel or an electronic paper using a flexible substrate. The problem of the display device of high temperature heat treatment.

再者，從資源性問題、以及對人體及/或環境的影響，殷切盼望不使用In及/或Ga的氧化物型半導體材料，從該觀點亦必須研發IGZO的代替材料。 Furthermore, from the viewpoint of resource problems and influence on the human body and/or the environment, it is eager to use an oxide semiconductor material of In and/or Ga, and from this viewpoint, it is necessary to develop an alternative material of IGZO.

就該IGZO的代替材料而言，例如有人提出由Zn氧化物與Sn氧化物所構成之氧化物型半導體材料(ZTO：Zn-Sn-O系氧化物)(專利文獻2、專利文獻3、專利文獻4、專利文獻5)。諸該先前技術的ZTO係研發用以實現高載子遷移率。在諸該先前技術中，雖得知可實現高載子遷移率， 惟並無針對形成TFT時之熱處理溫度進行充分地檢討，並未得知對有機EL面板及/或電子紙張的適用可能性。 An oxide-type semiconductor material (ZTO: Zn-Sn-O-based oxide) composed of a Zn oxide and a Sn oxide has been proposed as an alternative material for the IGZO (Patent Document 2, Patent Document 3, and Patent). Document 4, Patent Document 5). The prior art ZTO series was developed to achieve high carrier mobility. In the prior art, although it is known that high carrier mobility can be achieved, However, the heat treatment temperature at the time of forming the TFT was not sufficiently examined, and the possibility of application to the organic EL panel and/or the electronic paper was not known.

尤其，在專利文獻5中，雖提出在含有Zn及Sn之氧化物型半導體材料中，作為摻雜物使含有包括Zr之多數元素，從而形成使電子載子密度為大於1×1015/cm3小於1×1018/cm3的氧化物型半導體材料。惟對於該專利文獻5，雖針對薄膜(Sheet)電阻進行檢討，但並未充分地檢討形成TFT時的熱處理溫度及/或熱處理時之摻雜物的含有量等。在該專利文獻5中薄膜電阻與載子密度係具有下述之數式的關係。 In particular, in Patent Document 5, it is proposed that, in an oxide-type semiconductor material containing Zn and Sn, a plurality of elements including Zr are contained as a dopant, so that an electron carrier density of more than 1 × 10 15 /cm is formed. 3 an oxide type semiconductor material of less than 1 × 10 18 /cm 3 . However, in Patent Document 5, although the sheet resistance is reviewed, the heat treatment temperature at the time of forming the TFT and/or the content of the dopant at the time of heat treatment are not sufficiently reviewed. In Patent Document 5, the sheet resistance and the carrier density have the following equations.

Rs=ρ/t Rs=ρ/t

ρ=1/(e．N．μ) ρ=1/(e.N.μ)

(Rs：薄膜電阻值、ρ：比電阻值(體積電阻率)、N：載子密度、μ：載子遷移率、t：膜厚) (Rs: sheet resistance value, ρ: specific resistance value (volume resistivity), N: carrier density, μ: carrier mobility, t: film thickness)

換言之，如專利文獻5所述，當只得知薄膜電阻值時，而無法確定膜厚或載子遷移率時，即無法確定載子密度。由此可見，現狀為關於作為IGZO之代替材料的ZTO，亦引頸期盼進一步的改善。 In other words, as described in Patent Document 5, when only the sheet resistance value is known, and the film thickness or the carrier mobility cannot be determined, the carrier density cannot be determined. It can be seen that the current status of ZTO, which is a substitute for IGZO, is also expected to improve further.

(先前技術文獻) (previous technical literature) (專利文獻) (Patent Literature)

專利文獻1：日本專利4164562號說明書。 Patent Document 1: Japanese Patent No. 4,146,562.

專利文獻2：日本特開2009-123957號公報。 Patent Document 2: Japanese Laid-Open Patent Publication No. 2009-123957.

專利文獻3：日本特開2010-37161號公報。 Patent Document 3: Japanese Laid-Open Patent Publication No. 2010-37161.

專利文獻4：日本特開2010-248547號公報。 Patent Document 4: Japanese Laid-Open Patent Publication No. 2010-248547.

專利文獻5：日本特開2009-123957號公報。 Patent Document 5: Japanese Laid-Open Patent Publication No. 2009-123957.

本發明係為有鑑於前述情況所開發者，目的係為提供一種含有Zn氧化物與Sn氧化物、以及作為摻雜物之Zr的氧化物型半導體材料(ZTO：Zn-Sn-O系氧化物)，以作為IGZO的代替材料，該氧化物型半導體材料的載子遷移率為與IGZO同等以上者，為10cm2/Vs左右之高載子遷移率，並且不須300℃以上之高溫熱處理。 The present invention has been made in view of the foregoing circumstances, and an object thereof is to provide an oxide type semiconductor material (ZTO: Zn-Sn-O-based oxide) containing Zn oxide and Sn oxide, and Zr as a dopant. In the case of the IGZO, the carrier-type mobility of the oxide-type semiconductor material is equal to or higher than that of IGZO, and has a high carrier mobility of about 10 cm 2 /Vs, and does not require a high-temperature heat treatment of 300 ° C or higher.

為了解決前述課題，本發明人等，係針對在由Zn氧化物與Sn氧化物所構成之氧化物型半導體材料，使含有Zr以作為摻雜物之情形經深入研究，發現在預定範圍之摻雜物含有量中，於保持具有高載子遷移率狀態下，不必高溫熱處理即可實現能夠驅動TFT的ZTO膜。 In order to solve the above problems, the inventors of the present invention have conducted intensive studies on the case where an oxide-type semiconductor material composed of a Zn oxide and a Sn oxide is contained as a dopant, and found that it is doped in a predetermined range. Among the contents of the impurities, the ZTO film capable of driving the TFT can be realized without high-temperature heat treatment while maintaining the high carrier mobility.

本發明係為含有Zn氧化物與Sn氧化物之氧化物型半導體材料，該氧化物型半導體材料係含有Zr作為摻雜物，Zr含有量係為，相對於作為金屬元素之Zn、Sn、Zr之各原子數總和之摻雜物的原子比為0.005以下。 The present invention is an oxide type semiconductor material containing a Zn oxide and a Sn oxide, the oxide type semiconductor material containing Zr as a dopant, and the Zr content is Zn, Sn, Zr as a metal element. The atomic ratio of the dopant of the sum of the respective atomic numbers is 0.005 or less.

根據本發明之氧化物型半導體材料，能夠使載子遷移率為與IGZO同等以上，且可實現10cm2/Vs左右之載子遷移率，並且藉由250℃以下之熱處理，即形成TFT等之開關元件。此外，因不含有In、Ga，故亦無資源性之問題，且減少對人體及/或環境的影響。 According to the oxide-type semiconductor material of the present invention, the carrier mobility can be equal to or higher than that of IGZO, and a carrier mobility of about 10 cm 2 /Vs can be achieved, and a TFT or the like can be formed by heat treatment at 250 ° C or lower. Switching element. In addition, since it does not contain In and Ga, it has no resource problems and reduces the impact on the human body and/or the environment.

在本發明之氧化物型半導體材料之摻雜物的Zr，係相對於作為金屬元素之Zn、Sn、Zr之各原子數總和之摻雜物的原子比設為0.005以下。具體而言，係令作為金屬元素的Zn之原子數為x、Sn之原子數為y、Zr之原子數為z的情形下，以z/(x+y+z)≦0.005之方式含有摻雜物。該原子比若超過0.005，則在進行300℃之熱處理時載子密度變成未滿1×1015cm-3，而無法維持良好的半導體特性。若原子比為0.005以下，則因載子密度變成未滿1×1018cm-3，故可實現與350℃熱處理後之IGZO膜同等以下的載子密度。摻雜物含有量的下限值，係可實現與IGZO同等以下的載子密度，若藉由250℃以下之熱處理可形成TFT等之開關元件，則不侷限於該數值。在本發明人等的研究下，確認摻雜物之Zr含有量即便在原子比為0.000085(8.5×10-5)，亦可採用作為本發明之氧化物型半導體材料。 The atomic ratio of the dopant of the dopant of the oxide-type semiconductor material of the present invention to the sum of the respective atomic numbers of Zn, Sn, and Zr as the metal element is 0.005 or less. Specifically, when the number of atoms of Zn as a metal element is x, the number of atoms of Sn is y, and the number of atoms of Zr is z, z is added as z/(x+y+z)≦0.005. Sundries. When the atomic ratio exceeds 0.005, the carrier density becomes less than 1 × 10 15 cm -3 at the time of heat treatment at 300 ° C, and good semiconductor characteristics cannot be maintained. When the atomic ratio is 0.005 or less, the carrier density becomes less than 1 × 10 18 cm -3 , so that the carrier density equal to or lower than that of the IGZO film after heat treatment at 350 ° C can be achieved. The lower limit of the dopant content is a carrier density equal to or lower than that of IGZO, and a switching element such as a TFT can be formed by heat treatment at 250 ° C or lower, and is not limited to this value. The inventors of the present invention have confirmed that the Zr content of the dopant can be used as the oxide semiconductor material of the present invention even at an atomic ratio of 0.000085 (8.5 × 10 -5 ).

本發明之氧化物型半導體材料的Zn與Sn，在令Zn之金屬元素的原子數為A、令Sn之金屬元素的原子數為B時，較佳為以A/(A+B)=0.4至0.8之比率含有，更佳為0.6至0.7之比率。若該A/(A+B)未滿0.4，則Sn的比率會變高，故在蝕刻元件形成時所成膜的薄膜以進行圖案化時，利用草酸系蝕刻液的蝕刻速度會極端地變慢，不適於生產步驟。此外，若超過0.8，則因Zn的比率變高，故會使氧化物型半導體材料對於水之耐性變低，而在TFT元件的形成之際於一般性使用之配線及/或半導體層的圖案化步驟中，由於阻劑之剝離劑及/或純水洗淨之影響使 ZTO膜本身受到損壞，而使原本之TFT元件特性無法實現，且視情況的不同，ZTO膜會從基板溶解、脫落，而無法形成TFT元件。 In the oxide-type semiconductor material of the present invention, Zn and Sn are preferably A/(A+B)=0.4 when the number of atoms of the metal element of Zn is A and the number of atoms of the metal element of Sn is B. A ratio of up to 0.8 is contained, more preferably a ratio of 0.6 to 0.7. When the A/(A+B) is less than 0.4, the ratio of Sn becomes high. Therefore, when the film formed by the etching element is patterned, the etching rate of the oxalic acid-based etching solution is extremely changed. Slow, not suitable for production steps. In addition, when the ratio exceeds 0.8, the ratio of Zn becomes high, so that the resistance of the oxide semiconductor material to water is lowered, and the pattern of the wiring and/or the semiconductor layer which is generally used in the formation of the TFT element is formed. In the chemical step, the effect of the stripper and/or pure water washing of the resist is The ZTO film itself is damaged, and the characteristics of the original TFT element cannot be realized, and depending on the case, the ZTO film dissolves and falls off from the substrate, and the TFT element cannot be formed.

本發明之氧化物型半導體材料，係對底閘極型或者頂閘極型之薄膜電晶體非常地有效。如前述，根據本發明之氧化物型半導體材料，因可實現與IGZO同等以上的載子遷移率，且可使用在250℃以下之低溫熱處理，故為適合於要求高響應速度之立體顯示型的液晶顯示器，於形成利用可撓性基板等之有機EL面板及電子紙張等之開關元件時亦可適用。 The oxide-type semiconductor material of the present invention is very effective for a thin film transistor of a bottom gate type or a top gate type. As described above, the oxide-type semiconductor material according to the present invention is suitable for a stereoscopic display type requiring high response speed because it can achieve a carrier mobility equal to or higher than that of IGZO and can be used at a low temperature heat treatment of 250 ° C or lower. The liquid crystal display can also be applied to the formation of a switching element such as an organic EL panel or an electronic paper using a flexible substrate.

藉由本發明之氧化物半導體材料形成開關元件時，利用藉由該氧化物半導體材料所形成之薄膜係為有效，在用以成膜該薄膜時使用濺鍍法為佳。 When a switching element is formed by the oxide semiconductor material of the present invention, it is effective to use a thin film formed of the oxide semiconductor material, and a sputtering method is preferably used for forming the thin film.

而且，於藉由該濺鍍法形成本案發明之氧化物型半導體材料之薄膜時，使用屬於由Zn氧化物與Sn氧化物所構成，而且含有Zr，Zr含有量係相對於作為金屬元素之Zn、Sn、Zr之各原子數總和之摻雜物的原子比為0.005以下的濺鍍靶為佳。而且，Zn與Sn，係於令Zn之金屬元素的原子數為A、令Sn之金屬元素的原子數為B時，以使A/(A+B)=0.4至0.8之含有比率的靶材為佳。此時，在濺鍍之成膜時，即可使用直流電源或高頻電源、脈衝DC電源。尤其在使用靶材時，藉由使用脈衝DC電源，因能夠抑制產生於靶材表面之結粒或表面高電阻層之形成，而進行穩定之成膜，故成為適合於量產步驟。 Further, when the thin film of the oxide-type semiconductor material of the present invention is formed by the sputtering method, it is composed of Zn oxide and Sn oxide, and contains Zr, and the Zr content is relative to Zn as a metal element. It is preferable that the atomic ratio of the dopant of each of the sum of the atomic numbers of Sn and Zr is 0.005 or less. Further, Zn and Sn are those in which the atomic number of the metal element of Zn is A and the number of atoms of the metal element of Sn is B, so that the ratio of A/(A+B)=0.4 to 0.8 is contained. It is better. At this time, a DC power source, a high frequency power source, or a pulsed DC power source can be used for film formation by sputtering. In particular, when a target is used, by using a pulsed DC power source, stable formation of a film formed on the surface of the target or formation of a high-resistance layer on the surface can be suppressed, which is suitable for mass production.

在使用本發明之氧化物型半導體材料進行元件形成時，雖可藉由前述濺鍍法進行成膜，惟在此之外亦可適用脈衝雷射沉積法等濺鍍以外之成膜法。此外，於以塗佈半導體材料的奈米粒子分散於溶劑之分散液的方法、或噴墨法形成電路，亦能夠使用本發明之氧化物型半導體材料形成元件。 When the device is formed by using the oxide-type semiconductor material of the present invention, the film formation can be carried out by the above-described sputtering method, and a film formation method other than sputtering such as pulsed laser deposition may be applied. Further, the oxide-type semiconductor material forming element of the present invention can also be used in a method of forming a dispersion of a semiconductor material-coated nanoparticle dispersed in a solvent or an inkjet method.

根據本發明之氧化物型半導體材料，能夠實現與IGZO同等以上的載子遷移率，且以250℃以下之低溫熱處理，可形成TFT等之開關元件。此外，因不含有In、Ga，故亦無資源性之問題，亦能夠減低對人體及環境的影響。 According to the oxide-type semiconductor material of the present invention, a carrier mobility equal to or higher than that of IGZO can be achieved, and a low-temperature heat treatment of 250 ° C or lower can form a switching element such as a TFT. In addition, since it does not contain In and Ga, it has no resource problems and can reduce the impact on the human body and the environment.

以下，針對本發明之實施形態加以說明。首先針對關於本實施形態之氧化物型半導體材料的濺鍍靶(sputtering target)之製作加以說明。 Hereinafter, embodiments of the present invention will be described. First, the production of a sputtering target for the oxide semiconductor material of the present embodiment will be described.

靶材製作：分別量秤預定量之於大氣環境中，施以於500℃之煆燒的ZnO粉、大氣環境中，施以於1050℃之煆燒的SnO2粉、以及未煆燒的ZrO2粉，投入樹脂製容器(pot)(4L)而以球磨機(ball mill)混合。在該球磨機進行旋轉速130rpm、12小時混合時間之混合。然後，將混合粉以網目500微米(μm)、線徑315μm之篩子進行篩選。將去除粗粒分之過篩粒的混合粉，充填至ψ 100毫米(mm)之碳製沖壓模具，藉由熱壓(hot press)製作燒結體。熱壓條件係將Ar氣體流量設為3L/min，在加壓9.4MPa下昇溫至1050℃ 為止後，以加壓25Mpa下保持90分鐘，使之自然冷卻再取出燒結體。根據前述之順序，以進行用以形成為第1表所示之各原子比之薄膜的燒結體靶材之形成。 Target production: A predetermined amount of the scale is applied to the atmosphere, and the ZnO powder is sprayed at 500 ° C in an atmosphere, and the SnO 2 powder is applied at 1050 ° C and the ZrO is not burnt. 2 powder, put into a resin pot (4L) and mix with a ball mill. The ball mill was mixed at a rotation speed of 130 rpm and a mixing time of 12 hours. Then, the mixed powder was sieved with a sieve having a mesh size of 500 μm (μm) and a wire diameter of 315 μm. The mixed powder of the coarse-grained granules was removed, filled into a carbon-made press die of 毫米100 mm (mm), and a sintered body was produced by hot press. The hot pressing condition was such that the flow rate of the Ar gas was 3 L/min, and the temperature was raised to 1050 ° C under a pressure of 9.4 MPa, and then held at a pressure of 25 MPa for 90 minutes, and then naturally cooled and then the sintered body was taken out. According to the above procedure, formation of a sintered body target for forming a film of each atomic ratio shown in the first table is performed.

接著，針對使用已製作之燒結體的濺鍍靶的成膜方法、及其膜評估加以說明。使用市售之單片式濺鍍裝置(TOKKI公司製造：SML-464)進行成膜。濺鍍條件係設到達真空度1×10-5Pa，使用Ar/O2混合氣體作為濺鍍氣體，濺鍍氣壓設定在0.4Pa，氧分壓為0.01Pa，在室溫(25℃)的玻璃基板(日本電氣玻璃股份有限公司製造：OA-10)上，藉由150W之DC濺鍍，進行厚度約100奈米(nm)的成膜。 Next, a film formation method of a sputtering target using the produced sintered body, and a film evaluation thereof will be described. Film formation was carried out using a commercially available one-piece sputtering apparatus (manufactured by TOKKI Co., Ltd.: SML-464). The sputtering condition is set to a vacuum of 1 × 10 -5 Pa, and an Ar/O 2 mixed gas is used as a sputtering gas. The sputtering gas pressure is set at 0.4 Pa, and the oxygen partial pressure is 0.01 Pa at room temperature (25 ° C). On a glass substrate (manufactured by Nippon Electric Glass Co., Ltd.: OA-10), a film having a thickness of about 100 nm (nm) was formed by DC sputtering at 150 W.

該成膜的膜組成係使用ICP(電或耦合電漿)發光分光分析裝置(SII NanoTechnology股份有限公司製造：Vista Pro)進行。在第1表中，記載由Zn、Sn、Zr的量測值，計算出的Zn/(Zn+Sn)、以及Zr/(Zn+Sn+Zr)的原子比之值。另外，使用於薄膜電晶體(TFT)等之元件時，該氧化物型半導體材料的組成，係將元件切斷，以透射型電子顯微鏡(TEM)等一邊觀察該元件剖面，一邊鑑定氧化物型半導體材料層，以EDX分析該部分即可進行鑑定。 The film formation of the film formation was carried out using an ICP (Electrical or Coupling Plasma) luminescence spectroscopic analyzer (manufactured by SII NanoTechnology Co., Ltd.: Vista Pro). In the first table, the values of the atomic ratios of Zn/(Zn+Sn) and Zr/(Zn+Sn+Zr) calculated from the measured values of Zn, Sn, and Zr are described. In addition, when it is used for an element such as a thin film transistor (TFT), the composition of the oxide semiconductor material is cut off, and the cross section of the element is observed by a transmission electron microscope (TEM) or the like, and the oxide type is identified. A layer of semiconducting material can be identified by analyzing the portion by EDX.

然後，將成膜之各試料，在大氣環境中，於200℃、220℃、250℃、300℃進行1小時退火處理，並分別進行霍爾效應量測，以求得各試料的比電阻值、載子遷移率、載子密度。該霍爾效應量測係藉由市售的霍爾效應量測裝置(Nanometrics japan股份有限公司製造：HL5500PC)，使用裁剪出10mm×10mm四方之各試料進行。於第1表顯示各 試料的比電阻值、載子遷移率、載子密度的結果。另外，該成膜後的熱處理，與成膜時(濺鍍時)之基板溫度不同，為在成膜後一端固定而穩定之膜施加熱能量。例如，在專利文獻5之基板溫度係為在施加於成膜時之熱，藉由濺鍍而分散之原子在附著於基板時，隨著該基板溫度的上昇，使附著於基板之原子產生移動至較穩定處的現象。換言之，成膜時之基板溫度的控制，係為以濺鍍時之能量與基板溫度之熱能量的總和，使原子的再配置進行，決定膜之結晶狀態及/或配向性等，故與本申請案中成膜後之熱處理不同。 Then, each sample formed by film formation was annealed at 200 ° C, 220 ° C, 250 ° C, and 300 ° C for 1 hour in an atmospheric environment, and Hall effect measurements were respectively performed to obtain specific resistance values of the respective samples. , carrier mobility, carrier density. The Hall effect measurement was carried out by using a commercially available Hall effect measuring device (manufactured by Nanometrics japan Co., Ltd.: HL5500PC) using a sample cut out of 10 mm × 10 mm square. In the first table, each shows The results of the specific resistance value, carrier mobility, and carrier density of the sample. Further, the heat treatment after the film formation is different from the substrate temperature at the time of film formation (during sputtering), and thermal energy is applied to the film which is fixed and stabilized at one end after film formation. For example, the substrate temperature in Patent Document 5 is the heat applied to the film formation, and the atoms dispersed by the sputtering adhere to the substrate, and the atoms adhering to the substrate move as the temperature of the substrate rises. To a more stable phenomenon. In other words, the control of the substrate temperature during film formation is based on the sum of the energy of the energy at the time of sputtering and the temperature of the substrate, and the rearrangement of atoms is performed to determine the crystal state and/or alignment of the film. The heat treatment after film formation in the application is different.

TFT評估：將前述之膜設為通道層，使用金屬遮罩製作薄膜電晶體(TFT)。在第1圖中，係顯示已形成之TFT元件的剖面概略圖(A)及平面尺寸概略圖(B)。如第1圖(A)所示，TFT的形成係首先在玻璃基板10上成膜Al合金(厚度2000 Å)以作為閘極電極20。在此的濺鍍氣壓係以0.4Pa，進行輸入電力1000W之DC濺鍍。接著成膜SiNx(厚度3000 Å)以作為絕緣膜30。在此係藉由電漿CVD裝置(samco公司製造：PD-2202L)進行成膜，並於基板溫度350℃進行輸入電力250W之電漿CVD。原料氣體之流量係設為SiH4：NH3：N2=100cc：10cc：200cc。繼續成膜前述ZTO-ZrO2膜(厚度300 Å)以作為通道層40。在此的濺鍍氣壓係於0.4Pa下進行輸入電力150W之DC濺鍍。設通道的W/L=22。最後藉由ITO成膜源極電極50(厚度2000 Å)與汲極電極51(厚度2000 Å)。在此的濺鍍氣壓係於0.4Pa下，進行輸入電力 600W之DC濺鍍。針對依前述方式製作之TFT之元件尺寸係顯示於第1圖(B)。該第1圖(B)之各寬度的數值單位係為mm。 TFT evaluation: The above film was used as a channel layer, and a thin film transistor (TFT) was fabricated using a metal mask. In the first drawing, a schematic cross-sectional view (A) and a plan view (B) of the formed TFT element are shown. As shown in FIG. 1(A), the formation of the TFT first forms an Al alloy (thickness 2000 Å) on the glass substrate 10 as the gate electrode 20. The sputtering gas pressure here was DC sputtering at an input power of 1000 W at 0.4 Pa. Next, a film of SiNx (thickness 3000 Å) was formed as the insulating film 30. Here, film formation was carried out by a plasma CVD apparatus (manufactured by Samco Co., Ltd.: PD-2202L), and plasma CVD of input electric power of 250 W was performed at a substrate temperature of 350 °C. The flow rate of the material gas was set to SiH 4 : NH 3 : N 2 = 100 cc: 10 cc: 200 cc. The aforementioned ZTO-ZrO 2 film (thickness 300 Å) was continuously formed as the channel layer 40. The sputtering gas pressure here was DC sputtering with an input power of 150 W at 0.4 Pa. Let W/L=22 of the channel. Finally, a source electrode 50 (thickness 2000 Å) and a drain electrode 51 (thickness 2000 Å) were formed by ITO. The sputtering gas pressure here was 0.4 Pa, and DC sputtering of an input power of 600 W was performed. The component sizes of the TFTs fabricated as described above are shown in Fig. 1(B). The numerical unit of each width of the first figure (B) is mm.

針對已製作之TFT係藉由半導體分析裝置(Agilent Technologies公司製造：Semiconductor Device Analyzer B1500A)量測TFT的傳達特性。量測時所施加之汲極電壓(Vds)係為1至5V，閘極電壓(Vgs)的量測幅度係設-10至20V。在第2圖至第7圖係顯示量測TFT的傳達特性之結果。第2圖至第5圖係顯示實施例1(各熱處理溫度)時之TFT特性，第6圖係顯示比較例1(熱處理200℃)時之TFT特性，第7圖係顯示比較例2(熱處理)時之TFT特性。另外，在第2圖至第6圖中，縱軸左側係為汲極電流：Ids(A)值的對數軸，縱軸右側係為√Ids值之小數點表示軸。 The transmission characteristics of the TFT were measured by the semiconductor analysis device (manufactured by Agilent Technologies, Inc.: Semiconductor Device Analyzer B1500A) for the fabricated TFT. The threshold voltage (Vds) applied during the measurement is 1 to 5 V, and the magnitude of the gate voltage (Vgs) is set to be -10 to 20 V. Fig. 2 to Fig. 7 show the results of measuring the transmission characteristics of the TFT. Fig. 2 to Fig. 5 show the TFT characteristics in the case of Example 1 (each heat treatment temperature), Fig. 6 shows the TFT characteristics in Comparative Example 1 (heat treatment at 200 ° C), and Fig. 7 shows Comparative Example 2 (heat treatment) The TFT characteristics of the time. In addition, in FIGS. 2 to 6, the left side of the vertical axis is the logarithmic axis of the value of the drain current Ids (A), and the decimal point of the right side of the vertical axis is the axis of the √Ids value.

如第1表所示，Zr含有量如果為原子比0.000085(8.5×10-5)至0.00312(3.12×10-3)，則得知在200℃熱處理後膜的載子密度係落入1×1015cm-3以上未滿1×1018cm-3的範圍。此外，針對比較例2係於熱處理溫度300℃，使膜的載子密度為未滿1×1015cm-3。 As shown in Table 1, if the Zr content is 0.000085 (8.5 × 10 -5 ) to 0.00312 (3.12 × 10 -3 ), it is found that the carrier density of the film after heat treatment at 200 ° C falls within 1 × 10 15 cm -3 or more and less than 1 × 10 18 cm -3 range. Further, in Comparative Example 2, the heat treatment temperature was 300 ° C, and the carrier density of the film was less than 1 × 10 15 cm -3 .

此外，實施例1的情況，在各熱處理溫度之TFT特性，為如第2圖至第5圖所示之結果。此外，於第2表顯示在第2圖至第5圖之各TFT特性值之結果。另外，電場效應 遷移率μ，係為藉由形成TFT元件而量測TFT特性之結果所獲得的值，第1表的載子遷移率，係藉由已成膜之膜的霍爾效應量測所獲得之值。此外，S值係指為顯示電晶體之特性的次臨界擺幅值(subthreshold swing value)。 Further, in the case of Example 1, the TFT characteristics at the respective heat treatment temperatures are as shown in Figs. 2 to 5 . Further, the results of the TFT characteristic values in the second to fifth figures are shown in the second table. In addition, the electric field effect The mobility μ is a value obtained by measuring the characteristics of the TFT by forming a TFT element, and the carrier mobility of the first table is a value obtained by Hall effect measurement of the film which has been formed. . Further, the S value refers to a subthreshold swing value which is a characteristic of the display transistor.

如第2圖至第5圖及第2表所示，得知實施例1的情況，在全部的熱處理溫度中，on/off比為5位數，顯示為良好之TFT特性。惟，如第2圖，在實施例1的熱處理溫度200℃中，係在on/off之直線的斜度稍變緩和。此外，針對實施例2至5亦得知為同樣的TFT特性。對此，如第6圖所示，在無摻雜之比較例1(200℃)的情況，確認成為不on/off而不截止的元件，並未發揮開關元件其作為通道層的功能。然後，如第7所示，在比較例2(200℃)的情況，得知on/off的作用非常地弱，並未發揮作為通道層的功能。 As shown in FIGS. 2 to 5 and Table 2, in the case of Example 1, the on/off ratio was 5 digits at all the heat treatment temperatures, and it was found to be a good TFT characteristic. However, as shown in Fig. 2, in the heat treatment temperature of 200 ° C of Example 1, the slope of the line on the on/off was slightly moderated. Further, the same TFT characteristics were also known for Examples 2 to 5. On the other hand, as shown in FIG. 6, in the case of Comparative Example 1 (200 ° C) which was not doped, it was confirmed that the element was not on/off and not turned off, and the function of the switching element as the channel layer was not exhibited. Then, as shown in the seventh example, in the case of Comparative Example 2 (200 ° C), it was found that the effect of on/off was extremely weak, and the function as the channel layer was not exhibited.

(產業上之可利用性) (industrial availability)

本發明之氧化物型半導體材料係作為如立體顯示型液晶顯示器之開關元件的要求更高速的響應速度之TFT的構成材料極為有效。此外，本發明之氧化物型半導體材料 因能夠使用於低溫熱處理，故適合於利用可撓性基板等之有機EL面板及電子紙張，且從資源性問題、以及對人體及環境之影響的觀點亦具高產業上之利用價值。 The oxide-type semiconductor material of the present invention is extremely effective as a constituent material of a TFT which requires a higher speed response speed as a switching element of a stereoscopic display type liquid crystal display. Further, the oxide semiconductor material of the present invention Since it can be used for low-temperature heat treatment, it is suitable for use in an organic EL panel or an electronic paper such as a flexible substrate, and has high industrial value from the viewpoint of resource problems and influence on the human body and the environment.

10‧‧‧玻璃基板 10‧‧‧ glass substrate

20‧‧‧閘極電極 20‧‧‧gate electrode

30‧‧‧絕緣膜 30‧‧‧Insulation film

40‧‧‧通道層 40‧‧‧Channel layer

50‧‧‧源極電極 50‧‧‧Source electrode

51‧‧‧汲極電極 51‧‧‧汲electrode

第1圖(A)及(B)係為TFT之元件概略圖。 Fig. 1 (A) and (B) are schematic diagrams of elements of the TFT.

第2圖係為TFT特性之量測曲線(實施例1，200℃)。 Fig. 2 is a measurement curve of TFT characteristics (Example 1, 200 ° C).

第3圖係為TFT特性之量測曲線(實施例1，220℃)。 Fig. 3 is a measurement curve of TFT characteristics (Example 1, 220 ° C).

第4圖係為TFT特性之量測曲線(實施例1，250℃)。 Fig. 4 is a measurement curve of TFT characteristics (Example 1, 250 ° C).

第5圖係為TFT特性之量測曲線(實施例1，300℃)。 Fig. 5 is a measurement curve of TFT characteristics (Example 1, 300 ° C).

第6圖係為TFT特性之量測曲線(比較例1，200℃)。 Fig. 6 is a measurement curve of TFT characteristics (Comparative Example 1, 200 ° C).

第7圖係為TFT特性之量測曲線(比較例2，200℃)。 Fig. 7 is a measurement curve of TFT characteristics (Comparative Example 2, 200 ° C).

10‧‧‧玻璃基板 10‧‧‧ glass substrate

20‧‧‧閘極電極 20‧‧‧gate electrode

30‧‧‧絕緣膜 30‧‧‧Insulation film

40‧‧‧通道層 40‧‧‧Channel layer

50‧‧‧源極電極 50‧‧‧Source electrode

51‧‧‧汲極電極 51‧‧‧汲electrode

Claims (3)

一種氧化物型半導體材料，係含有Zn氧化物與Sn氧化物之氧化物型半導體材料，其特徵為：在令Zn之金屬元素的原子數為A、令Sn之金屬元素的原子數為B時，以A/(A+B)=0.4至0.8之比率含有，而且進一步含有Zr作為摻雜物，Zr含有量係為，令作為金屬元素的Zn之原子數為x、Sn之原子數為y、Zr之原子數為z的情形下，z/(x+y+z)≦0.005。 An oxide type semiconductor material which is an oxide type semiconductor material containing Zn oxide and a Sn oxide, characterized in that when the number of atoms of the metal element of Zn is A and the number of atoms of the metal element of Sn is B It is contained in a ratio of A/(A+B)=0.4 to 0.8, and further contains Zr as a dopant, and the Zr content is such that the number of atoms of Zn as a metal element is x, and the number of atoms of Sn is y. In the case where the number of atoms of Zr is z, z/(x+y+z)≦0.005. 一種薄膜電晶體，係使用申請專利範圍第1項所述的氧化物型半導體材料形成的底閘極型或頂閘極型之薄膜電晶體。 A thin film transistor is a bottom gate type or top gate type thin film transistor formed using the oxide type semiconductor material described in claim 1 of the patent application. 一種濺鍍靶，係含有Zn氧化物與Sn氧化物，在令Zn之金屬元素的原子數為A、令Sn之金屬元素的原子數為B時，以A/(A+B)=0.4至0.8之比率含有，而且；進一步含有Zr作為摻雜物，Zr含有量係為，令作為金屬元素的Zn之原子數為x、Sn之原子數為y、Zr之原子數為z的情形下，z/(x+y+z)≦0.005。 A sputtering target containing Zn oxide and Sn oxide. When the number of atoms of the metal element of Zn is A and the number of atoms of the metal element of Sn is B, A/(A+B)=0.4 The ratio of 0.8 is contained, and further, Zr is contained as a dopant, and the Zr content is such that when the number of atoms of Zn as a metal element is x, the number of atoms of Sn is y, and the number of atoms of Zr is z, z / (x + y + z) ≦ 0.005.
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