A Structural Study of Copper Oxide Grown on Cu(110) under Near Ambient Pressure Conditions

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梁銓軒(Quan-Xuan Liang) 查詢紙本館藏

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物理學系

論文名稱

(A Structural Study of Copper Oxide Grown on Cu(110) under Near Ambient Pressure Conditions)

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摘要(中)

在近常壓的氧氣壓力條件下，兩種不同型態的氧化銅已經被證實。初
始態的氧化銅與基板間的交互作用和隨著氣壓上升造成的結構變化都會影
響其催化能力。隨著由高真空至近常壓的氧氣壓力變化並控制在合適的
成長溫度 (550K)，藉由高能電子繞射 (RHEED)、掃描穿隧顯微鏡 (STM)
及常壓 X-ray 光電子能譜 (AP-XPS) 去觀察晶體結構和電子態的變化在銅(110) 表面。

在氧氣氣壓小於 10?5 托時，電子繞射結果顯示表面由 c(6 × 2) 和 (2 × 1) 共存態組成。隨著氧氣壓力處於 10?5 托至 10?2 托之間且曝氧量大於 1.8 × 104L，由繞射結果我們發現表面始終只有 c(6 × 2) 的結構出現，銅 2p 圖譜只表現出塊材的訊號也表明沒有氧化銅的形成。然而，氧 1s 圖譜顯示氧量的確上升。此外，在 STM 圖裡面，我們發現到平台上的高低起伏出現明顯的改變，從而推斷表面下有氧與銅形成鍵結導致此現象。當氧氣壓介於 10?2 托至 10?1 托之間，氧化亞銅逐漸佔據表面。而在初始階段時，氧化亞銅與 c(6 × 2) 共存時為雙重態且偏好向下生長。最終在 10?1托的氣壓下，氧化亞銅的厚度大約是 3.5 奈米且結構改變成非晶態，還伴隨著氧化銅的薄膜態。隨著增加氧氣壓力至大於 1 托時，由光譜我們可得知氧化銅厚度超過 3.41 奈米且強化學吸附的氧明顯增加。然而，在此氣壓下無法觀察到繞射結構，表示氧化銅的成長方式轉為無定型態。氧氣氣壓進一步調節到 5 托時，沒有新的銅化物出現。氧化銅厚度也沒有明顯變化，僅有強化學吸附的氧數量上的提升。

摘要(英)

Under near ambient oxygen pressure condition, there are two kinds of
copper oxide having been confirmed. The interaction between initial state of
copper oxide and substrate and the structure evolution with pressure increase
will influence the catalytic capability. With regulating the oxygen pressure
from high vacuum to near ambient pressure and controlling at moderate
growth temperature (550 K), we observe the changes of crystal structure
and electronic state on Cu(110) surface by reflective high energy electron
diffraction (RHEED), scanning tunneling microscopy (STM) and ambient
pressure X-ray photoelectron spectroscopy (AP-XPS).

When the oxygen pressure is below 10?5 Torr, the result from electron
diffraction demonstrates the surface is composed of the co-existence state of
c(6 × 2) and (2 × 1). As the oxygen pressure is regulated in the interval
between 10?5 Torr and 10?2 Torr and the oxygen exposure is greater than
1.8 × 104 L, only the structure c(6 × 2) appears on the surface from the
diffraction result and only the signal of bulk copper is captured in the Cu
2p spectrum which denotes that there is not the formation of copper oxide.
However, the oxygen 1s spectrum shows that the amount of oxygen does
increase. In addition, we found there was a significant undulation in the
terrace in the STM images, which led to the inference that this phenomenon
was caused by the formation of bonds between oxygen and copper under
the surface. When the oxygen pressure is in the interval between 10?2 Torr
and 10?1 Torr, Cu2O gradually occupies the surface. In the initial stage,
Cu2O is double phase when it coexists with c(6×2) and also prefers to grow
downward. Finally, at a pressure of 10?1 Torr, the thickness of Cu2O is about
3.5 nm and the structure changes to the amorphous state, accompanied by
thin film state of CuO. As the oxygen pressure is increased to greater than 1
Torr, from the spectrum we can see that the CuO thickness exceeds 3.41 nm
and the strongly chemisorbed oxygen increases significantly. However, no
diffraction structure can be observed at this pressure, which indicates that
the growth mode of CuO transfers to the amorphous state. The oxygen
pressure was further adjusted to 5 Torr, no new copper compounds appear.
The thickness of CuO has not changed significantly, only the amount of
strongly chemisorbed oxygen has increased.

關鍵字(中)

★ 銅(110)
★ 氧化銅
★ STM
★ APXPS
★ RHEED

關鍵字(英)

論文目次

1 Introduction 1
2 Literature Survey 3
2.1 The Properties of Two Distinct Reconstructions on Cu(110) . 3
2.1.1 The Mechanisms of Forming Process for Two Reconstructions . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1.2 The phase Transition between Two Distinct Reconstructions . . . . . . . . . . . . . . . . . . . . . . . . 7
2.2 CO Reaction on Low-index Copper Surfaces in Oxygen-Lean
Condition . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.3 The Properties of Cuprous and Cupric Oxide . . . . . . . . . 9
2.3.1 The Higher CO Adsorption Energy on Cu2O Surface
Grown on Cu(111) Compared with Metallic Cu . . . . 9
2.3.2 The Structure of Cu2O on Cu(110) and Its Band Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
2.3.3 The CO Reduction Operates on CuO with Different
Structures . . . . . . . . . . . . . . . . . . . . . . . . 15
xiv
2.3.4 The Structure and Band Structure of CuO . . . . . . 17
3 Experimental Apparatus and Procedures 18
3.1 Vacuum System . . . . . . . . . . . . . . . . . . . . . . . . . 18
3.2 Reflection High Energy Electron Diffraction (RHEED) . . . . 20
3.2.1 The Principle of Scattering and Diffraction Condition 21
3.2.2 RHEED System Operation . . . . . . . . . . . . . . . 23
3.3 Ambient Pressure- X-Ray Photoelectron Spectroscopy (APXPS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
3.3.1 Photoelectric Effect in Soft X-Ray Region . . . . . . . 24
3.3.2 The Principle of Synchrotron Radiation and The Endstation of AP-XPS in TLS 24A1 . . . . . . . . . . . . 26
3.3.3 Data Analysis and Thickness Estimation . . . . . . . 29
3.4 Scanning Tunneling Microscopy (STM) . . . . . . . . . . . . 30
3.4.1 The Theory of Scanning Tunneling Microscopy . . . . 31
3.4.2 The Model of RHK-UHV 300 . . . . . . . . . . . . . 34
3.4.3 STM Tip Preparation . . . . . . . . . . . . . . . . . . 35
xv
3.5 Experimental Procedure . . . . . . . . . . . . . . . . . . . . 37
4 Results 40
4.1 Cu(110) and Distinct Oxygen Induced Surface Reconstructions 40
4.2 Cuprous Oxide on Cu(110) . . . . . . . . . . . . . . . . . . . 51
4.2.1 3D Double Phase Cuprous Oxide . . . . . . . . . . . . 51
4.2.2 Amorphous State of Bulk Cuprous Oxide and Thin
Film of Cupric Oxide on Surface . . . . . . . . . . . . 58
4.3 Amorphous State of Bulk Cupric Oxide . . . . . . . . . . . . 63
4.4 Thermal Decomposition of Cupric Oxide and Cuprous Oxide 66
5 Discussion 71

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指導教授

羅夢凡(Meng-Fan Luo)

審核日期

2025-1-20

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