Copper Discoloration: Correlation between Copper

Oxidation States and Their Colors

Lee Wei Cheat*, Lim Saw Sing
Infineon Technology (Kulim) Sdn. Bhd., Kulim Hi Tech Park, Kedah Darul Aman, Malaysia.
*
Phone: +604 427 9711 Email: WeiCheat.Lee@infineon.com

Abstract- Here we report a novel approach on how to differentiate voltage of 5 keV. Atomic force microscope (AFM, Bruker
the copper oxidation state based on their colors. A series of D3100) was carried out to measure the surface roughness of the
analyses are carried out in order to determine the correlation samples. The roughness measurement was done using tapping
between the state of copper oxides and their colors by using X-ray mode at a scan rate of 0.5 Hz with a scanning area of 10 µm 2.
photoelectron spectroscopy (XPS). Our analysis results reveal that
Energy dispersive X-ray spectroscopy (EDX, Horiba EMAX
the light and dark brownish colored copper areas are formed by
different copper oxide compositions whereby dark colored copper 80 mm2) was carried out to check the elemental composition of
area consisted a mixture of Cu2O and CuO, whilst the light the copper at the light and dark brownish areas at an
colored copper area is dominated by Cu2O with trace of CuO. accelerating voltage of 5 keV. The chemical states of copper at
both light and dark brownish colored copper areas were
Keywords –Copper oxides, Dark brownish, Light brownish,
determined by using X-ray photoelectron spectroscopy (XPS,
CuO, Cu2O.
PHI Quantum 2000). The XPS analysis method for these
samples was small spot photoelectron spectroscopy (15 keV
I. INTRODUCTION with a spot size of 100 µm) combined by ion sputtering for
depth profiling (4 keV at a scan area of 2.6 x 2.6 mm2).
Copper is one of the metals that have been extensively used in
various fields including architecture, machined products, III. RESULTS AND DISCUSSION
telecommunications as well as semiconductors. One of the
reasons copper metal has attracted considerable attention in
diverse fields because of it is one of the earth-abundance
inexpensive metals exhibited reasonably good physical and
chemical properties such as high electrical conductivity,
ductility, low thermal expansion and high thermal conductivity
[1, 2]. Copper metal is stable at standard room temperature and
pressure and it is one of the few metals that occur in nature
directly usable metallic form [2]. It is a 3d transition metal and
it exists in a number of different oxidation states, including
monovalent (Cu+), divalent (Cu2+) or even trivalent (Cu3+) [3].
Although copper is stable, it does react slowly with atmospheric
oxygen to form copper oxide on the copper surface [4]. Other
than that, annealing temperature of copper will also lead to the
formation of a thin copper oxide layer on the copper surface [5,
6]. Three different types of copper oxides can be formed when
reacted with oxygen species, such as Cu2O (cuprous oxide),
CuO (cupric oxide) and Cu2O3 (copper (III) oxide) [8]. It has Fig. 1 (A) Optical and (B) SEM images of discolored copper area. High
been reported that pure Cu2O can be obtained at an annealing magnification SEM images of (C) dark brownish and (D) light brownish
temperature of 225°C, while pure CuO will form at an colored copper areas.
annealing temperature of 350°C [5]. Herein, we report a study
on the correlation between the copper oxidation states and their The typical topographies and surface morphologies of the
colors using XPS. light and dark brownish colored copper areas were inspected
under OM and SEM, as shown in Fig. 1. Under OM inspection,
II. EXPERIMENTS a clear droplet like dark brownish colored copper area was
Optical microscope (OM, Olympus MX61) was used to found on the copper surface, as shown in Fig. 1A. A clear
inspect the topography of discolored and non-discolored copper boundary was observed between the light and dark brownish
areas. After optical inspection, the light and dark brownish colored copper areas. SEM was used to investigate the surface
colored copper areas were manually cleaved into small piece, morphologies of the light and dark brownish colored copper
~20 mm2 for further analysis. Field emission scanning electron areas, as shown in Fig. 1B-D. Different from the observation of
microscopy (FESEM, Hitachi S4800) was used to investigate OM, at low magnification, the boundary between light
the surface morphologies of the samples at an accelerating brownish and dark brownish colored copper area was
indistinguishable under SEM inspection (Fig. 1B). Figure 1C
and 1D revealed that the surface morphologies of light and dark
brownish colored copper areas at high SEM magnification were
comparable.
Fig. 2 AFM topography images of (A) dark brownish and (B) light brownish
colored copper areas.
In order to check the surface roughness between these two
samples, AFM measurement was carried out. Fig. 2 shows the
topography images of the light and dark brownish colored
copper areas captured by AFM. The surface roughnesses (Rrms)
of the light and dark brownish colored copper areas were
measured to be 54.4 nm and 52.9 nm, respectively. The
measurements revealed that the surface roughness at these two
areas was comparable. Thus, we can rule out the copper
discoloration is not due to the different in surface roughness.
Fig. 3 EDX comparison spectra between the dark and light brownish areas at
5 keV, (A) overview and (B) zoomed in.
After confirming the copper discoloration is not caused by
the different in surface roughness, the next step is to check the
chemical compositions at the discolored copper areas. There are
a number of analytical tools that can be used to determine the
chemical composition of the light and dark brownish colored
copper areas. Energy dispersive X-ray spectroscopy (EDX) is
one of the widely used analytical tools to detect the chemical
composition of materials.
As presented in Fig. 3A, both the dark and light brownish
areas also detected the presence of high in Cu with small peaks
of C and O. It is noteworthy that in the zoomed in spectrum,
Fig. 3B, it demonstrated that the O peak intensity for the dark
brownish area is slightly higher as compared to that from light
brownish area. This EDX finding indicated that the dark and
light brownish areas are having copper oxide on the surface of
copper but with different compositions. Previous study had
demonstrated that EDX is not suitable to differentiate the type
of copper oxides [9], therefore XPS was used in order to
determine the chemical state of the copper at the light and dark
brownish colored copper areas.
Fig. 4 XPS Cu 2p peak fitting for (A) light brownish and (B) dark brownish
colored copper areas.
Fig. 4 showed the Cu 2p peak fitting graphs for light and dark
brownish colored copper areas. The results depicted the
presence of Cu, Cu(OH)2, Cu2O and CuO from both the light
and dark brownish colored copper areas. It is important to note
that there is a slightly different oxidation of copper was
observed between the light and dark brownish colored copper
areas although the concentration deviation of the different oxide
types is not really high, as shown in Fig. 4.
The atomic concentrations of copper at different chemical
states for light and dark brownish colored copper areas were
tabulated in Table 1. The results clearly indicated that at light
brownish colored copper area, a much higher concentration of Formation of Cupric Oxide (CuO) Semiconductor,” IOSR-Journal of
Cu2O was detected; conversely a mixture of CuO and Cu2O was Applied Physics, pp. 01-07, Dec 2013.
acquired at the dark brownish colored copper area. Both the [9] W. C. Lee and F. T. Siow., “Physical analysis approach to investigate
light and dark brownish colored copper areas are having wafer backside discoloration,” in Symposium on IPFA, July 2017.
comparable Cu(OH)2.
Table I – Comparison Table for Copper Atomic Concentration (at. %)
Calculated from Peak Fit for Light and Dark Brownish Colored Copper Areas.

Atomic Concentration (at %), Copper

Chemical State
Light Brownish Dark Brownish
Cu2O 6.88 3.07

Cu 0.91 1.56

CuO 0.92 2.37

Cu(OH)2 3.29 3.40

IV. CONCLUSION
In conclusion, the correlation between the copper oxidation
states and the colors of the copper oxides was demonstrated in
the paper. The difference between the light and dark brownish
colored copper area was due to presence of difference
concentration of copper oxide with different oxidation state.
For the dark brownish colored copper area consisted a mixture
of CuO and Cu2O, whilst the light brownish colored copper area
mainly dominated by the Cu2O with trace of CuO.

ACKNOWLEDGMENT
S. S. Lim and W. C. Lee would like to thank the members in
the laboratory for the continuous support.

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