JPH0959087A - Formation of thin film - Google Patents
Formation of thin filmInfo
- Publication number
- JPH0959087A JPH0959087A JP7217101A JP21710195A JPH0959087A JP H0959087 A JPH0959087 A JP H0959087A JP 7217101 A JP7217101 A JP 7217101A JP 21710195 A JP21710195 A JP 21710195A JP H0959087 A JPH0959087 A JP H0959087A
- Authority
- JP
- Japan
- Prior art keywords
- film
- glass substrate
- thin film
- film forming
- substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000010409 thin film Substances 0.000 title claims abstract description 47
- 230000015572 biosynthetic process Effects 0.000 title description 5
- 239000000758 substrate Substances 0.000 claims abstract description 64
- 239000010408 film Substances 0.000 claims abstract description 54
- 239000011521 glass Substances 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 27
- 238000000151 deposition Methods 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 9
- 238000000608 laser ablation Methods 0.000 claims description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 15
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001882 dioxygen Inorganic materials 0.000 abstract description 9
- 239000007864 aqueous solution Substances 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 3
- 238000005299 abrasion Methods 0.000 abstract 2
- 239000003513 alkali Substances 0.000 abstract 1
- 238000004061 bleaching Methods 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 10
- 238000004544 sputter deposition Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 4
- 229910001863 barium hydroxide Inorganic materials 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- -1 FgF2 Substances 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000010415 tropism Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
- Physical Vapour Deposition (AREA)
- Physical Deposition Of Substances That Are Components Of Semiconductor Devices (AREA)
- Surface Treatment Of Glass (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、薄膜形成方法、詳
しくは、ガラス基板上に成膜材料を堆積／結晶化して薄
膜を形成する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a thin film, and more particularly to a method for forming a thin film by depositing / crystallizing a film forming material on a glass substrate.
【０００２】[0002]
【従来の技術】近年、良質で高結晶性、高特性の強誘電
体及び圧電体の薄膜を形成する方法の一つとして、レー
ザアブレーション法が注目されている。レーザアブレー
ション法は、レーザ光を固体のターゲットに照射し、放
出された中性原子、分子、イオンを基板上に堆積／結晶
化して薄膜を形成する方法である。2. Description of the Related Art In recent years, laser ablation has attracted attention as one of the methods for forming thin films of ferroelectrics and piezoelectrics of high quality, high crystallinity and high characteristics. The laser ablation method is a method in which a solid target is irradiated with laser light and emitted neutral atoms, molecules, and ions are deposited / crystallized on a substrate to form a thin film.
【０００３】このレーザアブレーション法が注目されて
いるのは、主に以下の理由による。 （１）成膜室の外部からレーザ光が導入されるために成
膜室の内部を結晶の成長に適した雰囲気、圧力に調整で
きる。（２）ターゲットのみから成膜材料が放出される
ために不純物のない薄膜が得られる。（３）圧力、基板
温度、成膜速度等のパラメータを独立に選択できる。The reason why the laser ablation method has received attention is mainly due to the following reasons. (1) Since the laser light is introduced from the outside of the film forming chamber, the inside of the film forming chamber can be adjusted to an atmosphere and pressure suitable for crystal growth. (2) Since the film forming material is released only from the target, a thin film free from impurities can be obtained. (3) Parameters such as pressure, substrate temperature, and film formation rate can be independently selected.
【０００４】一方、薄膜形成方法としては、別にスパッ
タリング法、ＣＶＤ法等が知られている。そして、Ｚｎ
Ｏ薄膜の形成には、従来より、スパッタリング法あるい
はＣＶＤ法が採用されている。On the other hand, as a thin film forming method, a sputtering method, a CVD method and the like are known separately. And Zn
Conventionally, a sputtering method or a CVD method has been adopted for forming the O thin film.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、スパッ
タリング法やＣＶＤ法によって形成されるＺｎＯ薄膜
は、膜厚が薄い（具体的には約２００ｎｍ）と、結晶性
及び配向性が悪いという問題があった。特に、基板とし
てガラス基板を使用した場合には、ガラス基板がアモル
ファス基板であるため、膜厚が約２００ｎｍで、かつ配
向性の優れたＺｎＯ薄膜を基板上に形成することは不可
能であった。However, the ZnO thin film formed by the sputtering method or the CVD method has a problem that the crystallinity and orientation are poor when the film thickness is thin (specifically, about 200 nm). . In particular, when a glass substrate was used as the substrate, it was impossible to form a ZnO thin film having a film thickness of about 200 nm and excellent orientation on the substrate because the glass substrate was an amorphous substrate. .
【０００６】そこで、本発明の目的は、配向性が優れて
いる薄膜をガラス基板上に形成することができる薄膜形
成方法を提供することにある。Therefore, an object of the present invention is to provide a thin film forming method capable of forming a thin film having excellent orientation on a glass substrate.
【０００７】[0007]
【課題を解決するための手段】以上の目的を達成するた
め、本発明に係る薄膜形成方法は、ガラス基板表面をア
ルカリ金属又はアルカリ土類金属の少なくともいずれか
一方の元素を含む物質に晒した後、前記ガラス基板上に
成膜材料を堆積／結晶化して薄膜を形成することを特徴
とする。In order to achieve the above object, in the thin film forming method according to the present invention, the glass substrate surface is exposed to a substance containing at least one element of alkali metal and alkaline earth metal. Then, a film forming material is deposited / crystallized on the glass substrate to form a thin film.
【０００８】さらに、本発明に係る薄膜形成方法は、ガ
ラス基板表面に成膜材料と異なる材料からなる中間層を
設けた後、前記中間層上に成膜材料を堆積／結晶化して
薄膜を形成することを特徴とする。中間層の材料として
は、ＳｉＯ2、ＦｇＦ2、Ｎａ 2Ｏ等が用いられる。ガラ
ス基板上や中間層上に成膜材料を堆積させる方法として
は、レーザアブレーション法が好ましい。Further, the thin film forming method according to the present invention is
An intermediate layer made of a material different from the film-forming material is formed on the surface of the lath substrate.
After providing, depositing / crystallizing a film forming material on the intermediate layer
It is characterized by forming a thin film. As a material for the intermediate layer
Is SiO2, FgF2, Na 2O or the like is used. Gala
As a method of depositing film-forming materials on a substrate or intermediate layer
Is preferably a laser ablation method.
【０００９】[0009]
【発明の実施の形態】以下、本発明に係るＺｎＯ薄膜形
成方法の実施形態について添付図面を参照して説明す
る。 ［第１実施形態］図１はレーザアブレーション装置を示
す。この装置は、成膜室１０内にターゲット１５と基板
１６を所定の間隔で設置し、光源ユニット２０から放射
されたレーザ光Ｌをレンズ２１を介して窓部１１から成
膜室１０内に導入し、ターゲット１５を照射するように
構成されている。成膜室１０には成膜室１０内を真空に
するための排気口１２が設けられており、この排気口１
２に排気装置（図示せず）が連結されている。さらに、
成膜室１０内に酸素ガスを供給するためのガス供給管１
３が成膜室１０に連結されている。BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of a ZnO thin film forming method according to the present invention will be described below with reference to the accompanying drawings. [First Embodiment] FIG. 1 shows a laser ablation device. In this apparatus, a target 15 and a substrate 16 are installed in a film forming chamber 10 at a predetermined interval, and a laser beam L emitted from a light source unit 20 is introduced into a film forming chamber 10 through a window 21 from a window 11. Then, the target 15 is irradiated. The film forming chamber 10 is provided with an exhaust port 12 for making the inside of the film forming chamber 10 a vacuum.
An exhaust device (not shown) is connected to 2. further,
Gas supply pipe 1 for supplying oxygen gas into the film forming chamber 10
3 is connected to the film forming chamber 10.
【００１０】ターゲット１５としては、純度が９９．９
９９％のＺｎＯ粉末を約２００ｋｇ／ｃｍ2でプレス成
形した後、１０００℃の温度で２４時間焼成した焼結Ｚ
ｎＯターゲットが使用される。ＺｎＯターゲット１５は
成膜室１０内の中央付近に配置され、基板１６はＺｎＯ
ターゲット１５に平行に向かい合わせて配置される。Ｚ
ｎＯターゲットと基板１６の距離は３０ｍｍである。基
板１６としては、ガラス基板（コーニング社製、品番：
＃７０５９）が使用される。ガラス基板１６は、中性洗
剤にて５分間、純水にて５分間、アセトンにて５分間の
順に超音波洗浄される。The target 15 has a purity of 99.9.
Sintered Z obtained by press-molding 99% ZnO powder at about 200 kg / cm 2 and then firing at a temperature of 1000 ° C. for 24 hours
nO target is used. The ZnO target 15 is arranged near the center of the film forming chamber 10, and the substrate 16 is made of ZnO.
The target 15 is arranged parallel to and facing the target 15. Z
The distance between the nO target and the substrate 16 is 30 mm. As the substrate 16, a glass substrate (manufactured by Corning, product number:
# 7059) is used. The glass substrate 16 is ultrasonically cleaned in the order of 5 minutes with a neutral detergent, 5 minutes with pure water, and 5 minutes with acetone.
【００１１】次に、基板１６は１Ｎの水酸化ナトリウム
水溶液（液温度：４０℃）に１０分間あるいは１Ｎの水
酸化バリウム水溶液（液温度：４０℃）に１０分間浸漬
された後、基板１６の表面に付着したＮａやＢａが離脱
しない程度に軽く純水で洗浄された。次に、基板１６は
乾燥され、成膜室１０内にセットされる。成膜室１０内
を１×１０-6Ｔｏｒｒまで真空排気した後、酸素ガスを
所定の圧力になるまで成膜室１０内に供給する。酸素ガ
スを供給することは、以下の理由による。一般に、レー
ザアブレーション法によってガラス基板上に形成された
ＺｎＯ薄膜は、亜鉛と酸素の割合が１：１になりにく
く、酸素が若干不足した組成を有する。酸素ガス雰囲気
中で成膜すると、この酸素不足を解消することができる
からである。さらに、酸素ガスの一部（約８％）をオゾ
ナイザにてオゾン化した。オゾンは活性化されているた
め、ＺｎＯ薄膜の酸素不足解消効果が酸素より大きいか
らである。Next, the substrate 16 is immersed in a 1N sodium hydroxide aqueous solution (liquid temperature: 40 ° C.) for 10 minutes or in a 1N barium hydroxide aqueous solution (liquid temperature: 40 ° C.) for 10 minutes, and then the substrate 16 is immersed. The surface was washed with pure water so lightly that Na and Ba adhering to the surface did not come off. Next, the substrate 16 is dried and set in the film forming chamber 10. After the film forming chamber 10 is evacuated to 1 × 10 −6 Torr, oxygen gas is supplied into the film forming chamber 10 until a predetermined pressure is reached. The supply of oxygen gas is based on the following reasons. Generally, a ZnO thin film formed on a glass substrate by the laser ablation method has a composition in which the ratio of zinc and oxygen is less likely to be 1: 1 and oxygen is slightly insufficient. This is because if the film is formed in an oxygen gas atmosphere, this lack of oxygen can be eliminated. Furthermore, a part (about 8%) of the oxygen gas was ozonized with an ozonizer. This is because ozone is activated, and the effect of eliminating oxygen deficiency of the ZnO thin film is greater than that of oxygen.
【００１２】次に、ガラス基板１６を図示しないヒータ
にて所定の温度まで加熱した後、レーザ光ＬをＺｎＯタ
ーゲット１５に照射させる。光源ユニット２０として
は、ＡｒＦエキシマレーザが使用され、レーザ光Ｌは周
波数が５Ｈｚのパルスレーザで、ターゲット上でのエネ
ルギー密度が約１Ｊ／ｃｍ2のものである。レーザ光Ｌ
がＺｎＯターゲット１５を照射すると、ＺｎＯターゲッ
ト１５から中性原子、分子、イオン等の成膜材料である
小粒子が放出されプルームＰが形成される。放出された
成膜材料はガラス基板１６上に堆積し結晶化する。成膜
速度は、水晶振動式膜厚計でモニタしながら、４ｎｍ／
分を維持した。こうして、ガラス基板温度を５００℃に
設定すると共に、酸素ガス圧を６×１０-4に設定して、
膜厚が２００ｎｍのＺｎＯ薄膜を形成した。Next, the glass substrate 16 is heated to a predetermined temperature by a heater (not shown), and then the laser light L is irradiated on the ZnO target 15. An ArF excimer laser is used as the light source unit 20, and the laser light L is a pulse laser having a frequency of 5 Hz and an energy density on the target of about 1 J / cm 2 . Laser light L
When the ZnO target 15 is irradiated with, the small particles that are film forming materials such as neutral atoms, molecules, and ions are emitted from the ZnO target 15, and the plume P is formed. The released film forming material is deposited on the glass substrate 16 and crystallized. The film formation speed is 4 nm /
Hold the minute. Thus, while setting the glass substrate temperature to 500 ° C. and the oxygen gas pressure to 6 × 10 −4 ,
A ZnO thin film having a film thickness of 200 nm was formed.
【００１３】形成されたＺｎＯ薄膜は、Ｘ線回折法（θ
−２θ法、ロッキングカーブ法）により結晶構造と配向
性が評価された。その結果、形成されたＺｎＯ薄膜は、
ガラス基板１６上に〈００１〉軸が垂直に配向している
Ｃ軸配向膜であった。さらに、Ｃ軸配向性良さを評価す
るため、ガラス基板１６面に垂直な方向に対する〈００
１〉軸方向の揺らぎを、（００２）面からの回折ピーク
のロッキングカーブ半値幅の値で評価した。評価結果
は、表１が示すように、水酸化ナトリウム水溶液で処理
された基板１６の場合は半値幅が１．６゜、水酸化バリ
ウム水溶液で処理された基板１６の場合は半値幅が１．
８゜のＣ軸配向性の良好なＺｎＯ薄膜であった。表１に
は比較のためにガラス基板を水酸化ナトリウムや水酸化
バリウムの水溶液で処理しなかった場合のＺｎＯ薄膜の
半値幅測定結果も合わせて表示している。The formed ZnO thin film was analyzed by the X-ray diffraction method (θ
The crystal structure and orientation were evaluated by the -2θ method and the rocking curve method). As a result, the formed ZnO thin film is
It was a C-axis oriented film in which the <001> axis was oriented vertically on the glass substrate 16. Furthermore, in order to evaluate the good C-axis orientation, <00
1> The fluctuation in the axial direction was evaluated by the value of the rocking curve full width at half maximum of the diffraction peak from the (002) plane. As shown in Table 1, the evaluation results show that the half-width of the substrate 16 treated with the sodium hydroxide aqueous solution is 1.6 °, and the half-width of the substrate 16 treated with the barium hydroxide aqueous solution is 1.
The ZnO thin film had a good C-axis orientation of 8 °. For comparison, Table 1 also shows the half-width measurement results of the ZnO thin film when the glass substrate was not treated with an aqueous solution of sodium hydroxide or barium hydroxide.
【００１４】[0014]
【表１】 [Table 1]
【００１５】表１より、水酸化ナトリウムや水酸化バリ
ウムの水溶液でガラス基板１６の表面を処理することに
より、ＺｎＯ薄膜の半値幅が小さくなり、Ｃ軸配向性が
向上することがわかる。From Table 1, it can be seen that by treating the surface of the glass substrate 16 with an aqueous solution of sodium hydroxide or barium hydroxide, the full width at half maximum of the ZnO thin film becomes smaller and the C-axis orientation is improved.
【００１６】［第２実施形態］第２実施形態は、ＺｎＯ
薄膜を成膜する前に、ガラス基板表面に中間層を形成す
る方法について説明する。第２実施形態に使用されるレ
ーザアブレーション装置は、ターゲット１５を２個有す
ることを残して、前記第１実施形態に使用した装置と同
様のものであるため、構造についての詳細に説明は省略
する。[Second Embodiment] In the second embodiment, ZnO is used.
A method of forming an intermediate layer on the surface of a glass substrate before forming a thin film will be described. The laser ablation device used in the second embodiment is the same as the device used in the first embodiment except that it has two targets 15, and therefore detailed description of the structure is omitted. .
【００１７】２個のターゲット１５は成膜室１０外から
の遠隔操作によりその位置を移動可能な状態で成膜室１
０内に配置されている。一方のターゲット１５は前記第
１実施形態で説明した焼結ＺｎＯターゲットが用いられ
る。他方のターゲット１５は、純度が９９．９９９％の
ＳｉＯ2粉末を約２００ｋｇ／ｃｍ2でプレス成形した
後、１０００℃の温度で２４時間焼成した焼結ＳｉＯ2
ターゲットが用いられる。まず、ＳｉＯ2ターゲット１
５が基板１６に平行に向かい合わせて配置される。Ｓｉ
Ｏ2ターゲット１５と基板１６の距離は３０ｍｍであ
る。基板としては、ガラス基板（コーニング社製、品
番：＃７０５９）が使用される。ガラス基板１６は中性
洗剤にて５分間、純水にて５分間、アセトンにて５分間
の順に超音波洗浄された後、成膜室１０内にセットされ
る。The two targets 15 can be moved by remote control from the outside of the film forming chamber 10 so that the film forming chamber 1 can be moved.
0. As the one target 15, the sintered ZnO target described in the first embodiment is used. The other target 15 is sintered SiO 2 obtained by press-molding SiO 2 powder having a purity of 99.999% at about 200 kg / cm 2 and then firing it at a temperature of 1000 ° C. for 24 hours.
The target is used. First, the SiO 2 target 1
5 are arranged parallel to the substrate 16 and face each other. Si
The distance between the O 2 target 15 and the substrate 16 is 30 mm. A glass substrate (manufactured by Corning, product number: # 7059) is used as the substrate. The glass substrate 16 is ultrasonically cleaned in the order of 5 minutes with a neutral detergent, 5 minutes with pure water, and 5 minutes with acetone, and then set in the film forming chamber 10.
【００１８】次に、ガラス基板１６の温度を５００℃、
酸素ガス圧を６×１０-4Ｔｏｒｒに設定した後、レーザ
光ＬをＳｉＯ2ターゲット１５に照射してＳｉＯ2ターゲ
ット１５から成膜材料である小粒子を放射する。放射さ
れた成膜材料はガラス基板１６上に堆積する。こうし
て、膜厚が約１０ｎｍのＳｉＯ2中間層を形成する。そ
の後、ＳｉＯ2ターゲット１５を移動させて、替わりに
ＺｎＯターゲット１５にレーザ光Ｌを照射させる。Ｚｎ
Ｏターゲット１５から放射された成膜材料はＳｉＯ2中
間層上に堆積し結晶化する。成膜速度は４ｎｍ／分であ
り、膜厚は２００ｎｍとした。形成されたＺｎＯ薄膜
は、Ｘ線回折法により結晶構造と配向性が評価された。
その結果、形成されたＺｎＯ薄膜は、ガラス基板１６上
に〈００１〉軸が垂直に配向しているＣ軸配向膜であっ
た。さらに、Ｃ軸配向性良さを評価するため、ガラス基
板１６面に垂直な方向に対する〈００１〉軸方向の揺ら
ぎを（００２）面からの回折ピークのロッキングカーブ
半値幅の値で評価した。評価結果は、表２が示すよう
に、ＳｉＯ2中間層を設けた基板１６の場合は半値幅が
１．７゜のＣ軸配向性の良好なＺｎＯ薄膜であった。表
２には比較のためにＳｉＯ2中間層を設けなかった場合
のＺｎＯ薄膜の半値幅測定結果も合わせて表示してい
る。Next, the temperature of the glass substrate 16 is set to 500.degree.
After the oxygen gas pressure was set to 6 × 10 -4 Torr, radiated from the SiO 2 target 15 is irradiated with a laser beam L to the SiO 2 target 15 small particles which is a film-forming material. The emitted film forming material is deposited on the glass substrate 16. Thus, a SiO 2 intermediate layer having a film thickness of about 10 nm is formed. After that, the SiO 2 target 15 is moved, and instead, the ZnO target 15 is irradiated with the laser beam L. Zn
The film-forming material emitted from the O target 15 is deposited on the SiO 2 intermediate layer and crystallized. The film forming rate was 4 nm / min, and the film thickness was 200 nm. The crystal structure and orientation of the formed ZnO thin film were evaluated by the X-ray diffraction method.
As a result, the formed ZnO thin film was a C-axis oriented film in which the <001> axis was vertically oriented on the glass substrate 16. Further, in order to evaluate the goodness of the C-axis orientation, the fluctuation in the <001> axis direction with respect to the direction perpendicular to the surface of the glass substrate 16 was evaluated by the rocking curve half value width of the diffraction peak from the (002) plane. As a result of the evaluation, as shown in Table 2, in the case of the substrate 16 provided with the SiO 2 intermediate layer, it was a ZnO thin film having a half-width of 1.7 ° and good C-axis orientation. For comparison, Table 2 also shows the measurement results of the full width at half maximum of the ZnO thin film when the SiO 2 intermediate layer was not provided.
【００１９】[0019]
【表２】 [Table 2]
【００２０】表２より、ＳｉＯ2中間層を設けた基板１
６の場合は、ＺｎＯ薄膜の半値幅が小さくなり、Ｃ軸配
向性が向上することがわかる。一般に、ガラス基板１６
の表面には研磨等による微小な歪が存在しており、この
歪はＺｎＯ薄膜の結晶性、配向性に悪影響を与える。従
って、第２実施形態の方法によって形成されたＳｉＯ 2
中間層が、ガラス基板１６表面の歪みを小さくしてＺｎ
Ｏ薄膜の配向性、結晶性を向上させたと考えられる。From Table 2, SiO2Substrate 1 provided with an intermediate layer
In the case of 6, the half-width of the ZnO thin film becomes small and the C-axis
It can be seen that the tropism improves. Generally, the glass substrate 16
There is a minute strain due to polishing on the surface of
The strain adversely affects the crystallinity and orientation of the ZnO thin film. Obedience
Thus, the SiO formed by the method of the second embodiment. 2
The intermediate layer reduces the strain on the surface of the glass substrate 16 so that Zn
It is considered that the orientation and crystallinity of the O thin film were improved.
【００２１】［他の実施形態］なお、本発明に係る薄膜
形成方法は前記実施形態に限定するものではなく、その
要旨の範囲内で種々に変更することができる。ガラス基
板表面を処理する物質としては、ＮａやＢａを含む物質
以外に、ＬｉやＫやＲｂやＣｓやＦｒやＳｒやＲａを含
む物質であってもよい。さらに、これらアルカリ金属又
はアルカリ土類金属の元素を含む物質以外に、Ｂを含む
物質でガラス基板表面を処理してもよい。[Other Embodiments] The thin film forming method according to the present invention is not limited to the above embodiment, and can be variously modified within the scope of the invention. The substance for treating the surface of the glass substrate may be a substance containing Li, K, Rb, Cs, Fr, Sr or Ra other than the substance containing Na or Ba. Further, the surface of the glass substrate may be treated with a substance containing B other than the substance containing the element of alkali metal or alkaline earth metal.
【００２２】また、ガラス基板上や中間層上に成膜材料
を堆積させる方法としては、レーザアブレーション法が
好ましいが、必ずしもこれに限定するものではなく、Ｒ
Ｆスパッタリング法、ＥＣＲスパッタリング法、ＣＶＤ
法等を採用してもよい。さらに、中間層としては、Ｓｉ
Ｏ2膜以外に、Ｎａ2Ｏ膜、ＢａＯ膜等のアルカリ金属を
含む膜やアルカリ土類金属を含む膜、あるいはＭｇＦ2
膜等であっても同様の効果が得られる。さらに、これら
の膜はスパッタリング法、ＣＶＤ法等で基板表面に形成
してもよい。A laser ablation method is preferable as a method for depositing the film forming material on the glass substrate or the intermediate layer, but the method is not necessarily limited to this and R
F sputtering method, ECR sputtering method, CVD
The law may be adopted. Further, as the intermediate layer, Si
Besides the O 2 film, a film containing an alkali metal such as a Na 2 O film or a BaO film or a film containing an alkaline earth metal, or MgF 2
The same effect can be obtained with a film or the like. Further, these films may be formed on the surface of the substrate by a sputtering method, a CVD method or the like.
【００２３】また、成膜材料はＺｎＯ以外に、ＬｉＮｂ
Ｏ3、ＬｉＴａＯ3、ＰＺＴ等であってもよい。In addition to ZnO, the film forming material is LiNb.
It may be O 3 , LiTaO 3 , PZT or the like.
【００２４】[0024]
【発明の効果】以上の説明で明らかなように、本発明で
よれば、成膜前にガラス基板表面を、アルカリ金属又は
アルカリ土類金属の少なくともいずれか一方の元素を含
む物質に晒すことにより、ガラス基板上に結晶性、配向
性の良好な薄膜を形成することができる。また、成膜前
のガラス基板表面に、成膜材料と異なる材料からなる中
間層を設けることによっても、同様に結晶性、配向性の
良好な薄膜を形成することができる。As is apparent from the above description, according to the present invention, the glass substrate surface is exposed to a substance containing at least one element of alkali metal and alkaline earth metal before film formation. Thus, a thin film having good crystallinity and orientation can be formed on a glass substrate. Further, by providing an intermediate layer made of a material different from the film forming material on the surface of the glass substrate before film formation, a thin film having good crystallinity and orientation can be similarly formed.
【００２５】さらに、レーザアブレーション法によって
ガラス基板上や中間層上に成膜材料を堆積させることに
より、結晶性、配向性の著しく良好な薄膜が得られる。Further, by depositing a film forming material on the glass substrate or the intermediate layer by the laser ablation method, a thin film having extremely excellent crystallinity and orientation can be obtained.
【図１】本発明に係る薄膜形成方法に使用されるレーザ
アブレーション装置を示す概略図。FIG. 1 is a schematic view showing a laser ablation apparatus used in a thin film forming method according to the present invention.
Ｌ…レーザ光 １０…成膜室 １５…ＺｎＯターゲット １６…ガラス基板 L ... Laser light 10 ... Film forming chamber 15 ... ZnO target 16 ... Glass substrate
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｈ０１Ｌ 21/205 Ｈ０１Ｌ 21/205 41/18 Ｃ０３Ｃ 17/34 Ｚ // Ｃ０３Ｃ 17/34 Ｈ０１Ｌ 41/18 １０１Ｚ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical indication H01L 21/205 H01L 21/205 41/18 C03C 17/34 Z // C03C 17/34 H01L 41 / 18 101Z
Claims (4)
カリ土類金属の少なくともいずれか一方の元素を含む物
質に晒した後、前記ガラス基板上に成膜材料を堆積／結
晶化して薄膜を形成することを特徴とする薄膜形成方
法。1. A thin film is formed by exposing a surface of a glass substrate to a substance containing at least one element of an alkali metal and an alkaline earth metal and then depositing / crystallizing a film forming material on the glass substrate. And a method for forming a thin film.
からなる中間層を設けた後、前記中間層上に成膜材料を
堆積／結晶化して薄膜を形成することを特徴とする薄膜
形成方法。2. A method for forming a thin film, comprising forming an intermediate layer made of a material different from a film forming material on the surface of a glass substrate and then depositing / crystallizing the film forming material on the intermediate layer to form a thin film. .
る方法がレーザアブレーション法であることを特徴とす
る請求項１記載の薄膜形成方法。3. The thin film forming method according to claim 1, wherein the method of depositing the film forming material on the glass substrate is a laser ablation method.
法がレーザアブレーション法であることを特徴とする請
求項２記載の薄膜形成方法。4. The thin film forming method according to claim 2, wherein a method of depositing a film forming material on the intermediate layer is a laser ablation method.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7217101A JPH0959087A (en) | 1995-08-25 | 1995-08-25 | Formation of thin film |
| US08/696,149 US5741580A (en) | 1995-08-25 | 1996-08-13 | Crystalline thin film and producing method thereof, and acoustooptic deflection element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7217101A JPH0959087A (en) | 1995-08-25 | 1995-08-25 | Formation of thin film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0959087A true JPH0959087A (en) | 1997-03-04 |
Family
ID=16698869
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7217101A Pending JPH0959087A (en) | 1995-08-25 | 1995-08-25 | Formation of thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0959087A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002093822A (en) * | 2000-09-13 | 2002-03-29 | National Institute Of Advanced Industrial & Technology | MANUFACTURING METHOD OF SEMICONDUCTOR DEVICE HAVING ZnO-BASED OXIDE SEMICONDUCTOR LAYER |
| US6563174B2 (en) | 2001-09-10 | 2003-05-13 | Sharp Kabushiki Kaisha | Thin film transistor and matrix display device |
| JP2005537644A (en) * | 2002-08-28 | 2005-12-08 | モクストロニクス，インコーポレイテッド | Hybrid beam deposition system and method for fabricating metal oxide ZnO films, p-type ZnO films, and ZnO-based II-VI compound semiconductor devices |
| JP2009167095A (en) * | 2003-09-30 | 2009-07-30 | Nippon Mining & Metals Co Ltd | High purity zinc oxide powder, high purity zinc oxide target and high purity zinc oxide thin film |
-
1995
- 1995-08-25 JP JP7217101A patent/JPH0959087A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002093822A (en) * | 2000-09-13 | 2002-03-29 | National Institute Of Advanced Industrial & Technology | MANUFACTURING METHOD OF SEMICONDUCTOR DEVICE HAVING ZnO-BASED OXIDE SEMICONDUCTOR LAYER |
| US6563174B2 (en) | 2001-09-10 | 2003-05-13 | Sharp Kabushiki Kaisha | Thin film transistor and matrix display device |
| JP2005537644A (en) * | 2002-08-28 | 2005-12-08 | モクストロニクス，インコーポレイテッド | Hybrid beam deposition system and method for fabricating metal oxide ZnO films, p-type ZnO films, and ZnO-based II-VI compound semiconductor devices |
| JP4787496B2 (en) * | 2002-08-28 | 2011-10-05 | モクストロニクス，インコーポレイテッド | Hybrid beam deposition system and method and semiconductor device made thereby |
| JP2009167095A (en) * | 2003-09-30 | 2009-07-30 | Nippon Mining & Metals Co Ltd | High purity zinc oxide powder, high purity zinc oxide target and high purity zinc oxide thin film |
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