Electrochimica Acta 390 (2021) 138798

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

A critical review of fundamentals and applications of electrochemical

development and imaging of latent fingerprints
Chuanjun Yuan a,b,∗, Ming Li a,b, Meng Wang a,b, Haijun Cao c, Tianchun Lin c
a
College of Forensic Sciences, Criminal Investigation Police University of China, Shenyang 110035, China
b
Research Center of Crime Governance in the New Era, Criminal Investigation Police University of China, Shenyang 110035, China
c
Huadu District Branch, Guangzhou Municipal Public Security Bureau, Guangzhou 510810, China

a r t i c l e i n f o a b s t r a c t

Article history: Latent fingerprints containing morphological and biochemical information are one of the most important
Received 9 May 2021 evidence existed at crime scenes that can be used for personal identification. Despite some traditional
Revised 6 June 2021
development and imaging methods, various novel methods based on different principles have been ex-
Accepted 14 June 2021
plored to visualize latent fingerprints in recent years, among which many interesting methods estab-
Available online 22 June 2021
lished by using electrochemical techniques have proved to be very efficient. Up to now, a number of
Keywords: electrochemical systems have been utilized to create or detect the disparity between fingerprint ridge
Latent fingerprint area and background area, resulting in sensitive development and imaging of latent fingerprints. In this
Fingerprint development review, we highlight the recent progress in electrochemical development and imaging of latent finger-
Fingerprint imaging prints. To be specific, the introduction of fundamentals and applications of this research area is separated
Forensic science into four main sections: fingerprint development by electrochemical deposition, fingerprint imaging by
Electrochemistry
electrochemiluminescence (ECL), fingerprint imaging by scanning probe electrochemistry techniques, and
fingerprint analysis using other electrochemical methods. Finally, our perspectives on future research di-
rections are also presented and discussed.
© 2021 Elsevier Ltd. All rights reserved.

1. Introduction taminants in fingerprint residues can sometimes provide valuable

Fingerprints are impressions formed when friction ridge skin
on hands comes in contact with the surface of an object. They
have been used to determine the identity of individuals since the
late 19th century because they usually contain morphological in-
formation reflecting three levels of features on the friction ridge
skin [1,2]. The first-level features refer to general patterns reveal-
ing overall flow of papillary ridges. The second-level features, also
known as minutia, are the characteristic points of identification.
The third-level features refer to the shape of each ridge and sweat
pore, and relative positions of sweat pores. On the other hand, fin-
gerprint residues left on object surface also store some biochem-
ical information since they generally consist of both endogenous
and exogenous substances [3]. Sweat and sebum that are respec-
tively secreted by eccrine glands and sebaceous glands are the
most common endogenous substances, while various kinds of con-
taminants such as blood, dust, grease, cosmetics, drugs and explo-
sives that may stick to the friction ridge skin are potential exoge-
nous substances. It is noteworthy that certain metabolites and con-
∗
Corresponding author.
E-mail address: yuancj11@mails.jlu.edu.cn (C. Yuan).
information for forensic investigation and safety inspection [4,5].
More importantly, DNA can be obtained and used for individual
identification if there is a certain number of epidermal cells in fin-
gerprint residues that are sufficient for forensic DNA typing [6]. As
a result, fingerprints found at crime scenes are widely regarded as
one of the most critical physical evidence for crime detection and
investigation, considering the forensic significance of morphologi-
cal and biochemical information that may be contained within a
fingerprint.
There are two main categories of fingerprints according to the
degree of visibility to the unaided eye, namely visible fingerprints
and latent fingerprints. The visible fingerprints, as the term sug-
gests, are directly visible with no need for additional treatment,
while the latent fingerprints that are less visible or invisible are the
most common form of fingerprint evidence encountered at crime
scenes, so some sort of processing relying on optical, physical or
chemical techniques is normally required before inspection and
identification [7-9]. Traditional methods that are frequently used
to visualize latent fingerprints include powder dusting, cyanoacry-
late fuming, vacuum metal deposition, ninhydrin, 1,2-indanedione,
etc. [10-12]. These methods have been established to deal with la-
tent fingerprints formed under different conditions, including di-

https://doi.org/10.1016/j.electacta.2021.138798
0013-4686/© 2021 Elsevier Ltd. All rights reserved.
C. Yuan, M. Li, M. Wang et al. Electrochimica Acta 390 (2021) 138798

verse chemical composition of substances transferred at the mo-

ment of deposition and varied substrate surfaces which can be
classified into three categories—porous surfaces, semi-porous sur-
faces or non-porous surfaces—based on their interaction with the
deposited substances. But in spite of the widespread use of these
traditional methods, there are still some problems, caused by lim-
ited development sensitivity or inevitable damage to fingerprint
residues, that may seriously impact the effective acquisition of
morphological and biochemical information of latent fingerprints
[13,14]. Therefore, exploration of new and efficient methods has al-
ways been a popular research area in forensic science and related
fields, such as chemistry, physics and materials science. In recent
years, numerous studies that focus on the development and imag-
ing of latent fingerprints utilizing novel materials and advanced
equipment have been performed [15-17]. Accordingly, a number of
review articles summarizing these studies have been published up
to now. Just to give a few examples: Hazarika et al. [18] have sum-
marized various methods for detection and analysis of fingerprints
that are capable of synchronously providing the individual iden-
tity and chemical information. Wang et al. [19] have highlighted
recent progress in background-free imaging of latent fingerprints.
Prasad et al. [20] have reviewed the key role of nanotechnology in
the detection and development of latent fingerprints. Chávez et al.
[21] have presented a summary of phosphorescent and fluorescent
phosphors used in the detection of latent fingerprints.
The basic principle of development and imaging of latent fin-
gerprints is to create a disparity between fingerprint ridge area and
background area that can be recognized by the unaided eye or cer-
tain instruments, for instance, a digital camera. In fact, the dispar-
ity can be created or detected by some electrochemical techniques.
There are many advantages to introducing electrochemistry into
this area, including enhanced development sensitivity, good con-
trollability, low toxicity, and good compatibility with other meth-
Fig. 1. Electrochromic enhancement of sebaceous fingerprints on stainless steel
ods of analysis. Over the past two decades, lots of electrochemical
substrates. Images of developed fingerprints by polyaniline deposition captured at
methods for fingerprint development and imaging have been in- (a) −0.2, (b) 0.3 and (c) 0.9 V vs. SCE, and by Co3 O4 deposition captured at (d) −0.1,
vestigated. So, it is necessary to summarize the recent advances in (e) 0.6 and (f) −0.1 (reverse scan) V vs. Hg/HgO. (g) DNA analysis of fingerprint sam-
this research area, especially from the perspectives of fundamen- ples electrochemically treated with Co3 O4 system. (a-c) Reprinted with permission
tals and applications. According to the electrochemical techniques from Ref. [25]. Copyright 2010, American Chemical Society. (d-g) Reprinted with
permission from Ref. [31]. Copyright 2021, Elsevier.
that have been utilized, the discussion is divided into four sec-
tions: (i) fingerprint development by electrochemical deposition,
(ii) fingerprint imaging by ECL, (iii) fingerprint imaging by scan- ical deposition systems have been explored for this specific ap-
ning probe electrochemistry techniques, and (iv) fingerprint analy- plication. According to the chemical properties of electrodeposits,
sis using other electrochemical techniques. polymers (polyaniline, poly(3,4-ethylenedioxythiophene) (PEDOT),
polypyrrole, poly(2,2 :5 ,2 -terthiophene) (PTTh), etc.), metal ox-
2. Fingerprint development by electrochemical deposition ides (Co3 O4 , ZnO–CuO), metals (Au, Ag, Cu, Ni, etc.) and some other
materials (Prussian blue and graphene) have been investigated for
Electrochemical deposition is a conventional technique for the development and enhancement of latent fingerprints on con-
preparing functional films or electrode materials. In a typical de- ductive substrates. On the other side, electrochemical properties of
position process, precursors in electrolytes are electrochemically the substrates must also be taken into account, for some metal-
reduced or oxidized on the working electrode surface, gradually lic substrates may be affected (corroded or passivated) by certain
forming a solid-state film. Electron transfer between the elec- deposition systems. Therefore, fingerprint development by elec-
trolyte and the working electrode surface can be blocked by trochemical deposition will be classified based on the deposition
an insulating deposit of a few nanometers thick. Typical finger- protocol, namely anodic deposition, cathodic deposition and cyclic
print residues (ranging from 10 nm to 2 μm thick, depending voltammetric deposition.
on conditions [22])—especially ones containing lipids—are more
than sufficient to achieve this. For this reason, fingerprints de- 2.1. Fingerprint development by anodic deposition
posited on conductive substrates would locally “mask” the sur-
face and electrochemical products would deposit solely on unaf- Anodic depositions of polymers and transition metal oxide
fected area. Consequently, such kind of latent fingerprints can be have been explored for fingerprint development and enhancement.
developed by means of visual contrast between fingerprint ridge Beresford et al. [25] studied visualization of latent fingerprints on
area and background area resulted from the electrochemical de- stainless steel substrates through anodic deposition of polyaniline.
position. This way of developing latent fingerprints is very simi- As shown in Fig. 1(a)-(c), optical characteristics of the polyani-
lar to gun blueing and palladium deposition which are two tra- line deposited on background area can be continuously and re-
ditional methods based on chemical deposition of metals or al- versibly adjusted by varying the applied potential. Accordingly, vi-
loys onto conductive background area utilizing fingerprint ridge sual contrast of the developed fingerprints can be easily optimized.
area as a “mask” [23,24]. As listed in Table 1, many electrochem- This is the first study that focuses on utilizing electrochromism to

2
C. Yuan, M. Li, M. Wang et al. Electrochimica Acta 390 (2021) 138798

Table 1
Summary of fingerprint development by electrochemical deposition.

Fingerprint sample / substrate Electrodeposition system Applied potential Refs.

Sebaceous or eccrine fingerprints / stainless Polyaniline 0.9 V vs. SCE [25]

steel
Sebaceous or eccrine fingerprints / stainless PEDOT 0.9–1.2 V vs. Ag/AgCl [26]
steel
Sebaceous or eccrine fingerprints / brass PEDOT 0.9 V vs. Ag/AgCl [27]
cartridge cases
Sebaceous fingerprints / stainless steel Polyaniline or PEDOT 0.9 V vs. Ag/AgCl [28]
Sebaceous fingerprints / stainless steel Poly(pyrrole-co-EDOT) 0.7–1.0 V vs. Ag/AgCl [29]
Sebaceous fingerprints / stainless steel (Polypyrrole or PEDOT)/PTTh 0.9 V vs. Ag/AgCl and 0.8 V vs. Ag/Ag+ [30]
Sebaceous fingerprints / stainless steel Co3 O4 1.0 V vs. SCE [31]
Sebaceous or eccrine fingerprints / ITO, gold, Gold −0.5– −0.3 V vs. Ag/AgCl [32]
platinum, or stainless steel Silver −0.15 –0 V vs. Ag/AgCl
Sebaceous or eccrine fingerprints / ITO, gold, Copper −0.45– −0.16 V vs. Ag/AgCl [33]
platinum, silver, copper, or stainless steel
Sebaceous or natural fingerprints / ITO, Silver-copper alloy −0.7– −0.6 V vs. Ag QRE [34]
magnesium, zinc, copper, or stainless steel
Sebaceous fingerprints / copper Nickel/phosphors −0.65 V vs. RHE [35]
Sebaceous fingerprints / aluminum, copper, ZnO-CuO −0.8– −0.7 V vs. Ag/AgCl [36]
zinc, or stainless steel
Sebaceous fingerprints / ITO, aluminum, Graphene (−1.6– −0.6) to (0–0.5) V vs. Ag/AgCl [37]
stainless steel, magnesium, or zinc
Sebaceous fingerprints / ITO or stainless steel Prussian blue −0.1 to 1.2 V vs. Ag/AgCl [38]
Natural fingerprints / Prussian blue-coated Prussian blue −0.2 to 1.2 V vs. Ag/AgCl [39]
ITO
Sebaceous fingerprints / platinum, gold, silver, Polypyrrole 0 to 1.4 V vs. Ag/AgCl [40]
or Ergal alloy Poly(substituted porphyrin) 0 to 1.2 V vs. Ag/AgCl
Concept design / gold Poly(substituted pyrrole) 0.3 to 1.15 V vs. Ag/AgCl [41]

enhance latent fingerprints. Then, electrochromic enhancement of
fingerprints developed by electrodeposition of PEDOT was inves-
tigated by Brown et al. [26] The PEDOT film was anodically de-
posited from an aqueous electrolyte by using sodium dodecyl sul-
fate (SDS) to solubilize the EDOT monomer. Both potentiodynamic
and potentiostatic methods have been explored for the polymer-
ization of EDOT. In terms of image contrast of developed finger-
prints, potentiostatic method can give much better results. Costa
et al. [27] found that sebaceous, eccrine and aged fingerprints on
brass cartridge cases could be effectively visualized by electrodepo-
sition of PEDOT, although simultaneous corrosion of brass surface
also occurred during anodic deposition. Beresford et al. [28] pre-
sented a comprehensive study that compared the development and
enhancement of latent fingerprints on stainless steel substrates us-
ing electrochromic enhancement methods (polyaniline and PEDOT)
with three traditional development methods (powder dusting, wet
powder and cyanoacrylate fuming). Latent fingerprints collected
from different donors and exposed to different environments have
been used as test samples. The results of the experiment indi-
cate that the electrochromic enhancement methods frequently out-
perform the traditional methods, especially for samples that have
been exposed to more challenging environments. Electrochromic
enhancement approach was extended further from homopolymer
to co-polymer deposition by Sapstead et al. [29] Most experiments
have been performed using potentiostatic anodic deposition be-
cause it provides simplification of fixed-rate constants for the ox-
idation of pyrrole and EDOT. Image contrast of developed finger-
prints varies with co-monomer feedstock, deposition potential, and
applied potential after transfer to monomer-free background elec-
trolyte (an aqueous solution containing 0.2 M LiClO4 and 0.04 M
SDS). Costa et al. [30] proposed a fingerprint development strat-
egy based on electrodeposition of a bilayer system. The first layer
is polypyrrole or PEDOT that is electrodeposited onto background
area from aqueous solutions containing LiClO4 and correspond-
ing monomer. The second layer is fluorescent PTTh that is elec-
trodeposited onto the first layer from a CH3 CN solution contain-
ing 2,2 :5 ,2 -terthiophene (TTh) and (C4 H9 )4 NBF4 . Under UV light,
the background area can emit orange fluorescence due to the pres-
ence of PTTh in neutral state. However, this fluorescence develop-
ment can only be considered a good concept, for the second step
of electrodeposition shows no real improvement in visualization of
fingerprints, even for the fluorescence mode.
Our group investigated anodic deposition of electrochromic
Co3 O4 for development and enhancement of latent fingerprints
[31]. Image contrast and development accuracy during electrode-
position of Co3 O4 have been systemically evaluated. As shown in
Fig. 1(d)-(f), electrochromic properties of Co3 O4 can be used to re-
versibly adjust the image contrast of developed fingerprints, which
has been qualitatively and quantitatively analyzed through visual
appraisal and color channels, respectively. More importantly, as
shown in Fig. 1(g), the relatively non-destructive nature of this
electrochemical development and enhancement method has been
verified by forensic DNA analysis.
2.2. Fingerprint development by cathodic deposition
Up to now cationic depositions of metals (e.g., gold, silver, and
copper) and metal- or metal oxide-based composites (e.g., silver-
copper alloy, nickel/phosphors, and ZnO–CuO) have been inves-
tigated to develop fingerprints on various conductive substrates.
They can be used to process fingerprint samples on active metal
substrates owing to cathodic protection effect. For each system,
applied potential is selected based on the reduction potential of
the deposit on a specific substrate. Cathodic depositions of gold
from electrolyte containing AuCl4 − and silver from electrolyte con-
taining Ag+ have been utilized by Qin et al. [32] for the develop-
ment of sebaceous and eccrine fingerprints on various conductive
substrates. Considering only a small portion of metal salts in the
electrolyte can be actually used during the electrochemical depo-
sition, the utilization of noble metal salts raises the cost of finger-
print development. Besides, the electrolyte used for cathodic de-
position of gold contains 0.5 M H2 SO4 , which may corrode many
types of metal substrates and destroy trace evidence in finger-
print residues. A lower-cost alternative using cathodic deposition
of copper was proposed by Zhang et al. [33] Deposition param-
eters including concentration of Cu2+ , deposition time and depo-

3
C. Yuan, M. Li, M. Wang et al.
sition potential have been studied to optimize the development
effectiveness of sebaceous and eccrine fingerprints on conductive
substrates. Nevertheless, the electrolyte still contains 0.1 M H2 SO4
and the deposits are easily oxidized in air.
In addition to cathodic deposition of metals, cathodic depo-
sition systems of some composites have also been explored for
fingerprint development. Zhang et al. [34] reported a develop-
ment method based on cathodic deposition of silver-copper al-
loy in an electrolyte using deep eutectic solvent. This deep eu-
tectic solvent was prepared by mixing choline chloride with ethy-
lene glycol in a molar ratio of 1:2 at 60 °C. The resultant deposits
on background area are deep brown in color, allowing good con-
trast of developed fingerprint images. A cathodic composite depo-
sition of nickel/phosphors proposed by Zhang et al. [35] was used
to develop sebaceous fingerprints on copper substrates. Commer-
cial phosphors based on SrAl2 O4 were suspended in aqueous elec-
trolyte containing Ni2+ , which was stabilized by the addition of
boracic acid and surfactant. Original intention of this study is to
deposit nickel/phosphors on background area, resulting in a flu-
orescent background under illumination with 365 nm UV light.
However, from the fluorescence images of developed fingerprints,
it seems that the phosphors adsorbed on fingerprint ridges rather
than deposited along with nickel on background area. Zhang et al.
[36] reported another cathodic deposition method relying on co-
deposition of ZnO–CuO. A relatively high temperature of 65 °C is
required to deposit this metal oxide composite. A possible deposi-
tion mechanism is as follows:
NO3 − + H2 O + 2e → 2OH− + NO2 − (1)
M2+ + 2OH− → M(OH)2 (M = Zn or Cu) (2)
M(OH)2 → MO + H2 O (3)
2.3. Fingerprint development by cyclic voltammetric deposition
Cyclic voltammetric depositions of graphene, Prussian blue
and some polymers have been studied as new ways for finger-
print development so far. Using an aqueous electrolyte containing
graphene oxide colloids as the precursor, Zhang et al. [37] proved
that electrochemical reduction of graphene oxide to graphene
could also be utilized to develop sebaceous fingerprints on con-
ductive substrates. Scan rate and developing time have been opti-
mized to achieve better development of latent fingerprints. Since
the color of resultant graphene deposited on background area is
very dark, images of the developed fingerprints show very high
contrast.
Electrodeposition of Prussian blue by using cyclic voltammetry
was studied by Qin et al. [38] to develop sebaceous fingerprints
on ITO and stainless steel substrates. Cycle number has been in-
vestigated as a key parameter for fingerprint development. This
method may lead to overdevelopment because Prussian blue is
easily grown across the fingerprint ridges, which can be attributed
to the relatively fast rate of deposition. Ding et al. [39] explored
the application of Prussian blue-coated ITO electrode in fingerprint
collection. A compact and uniform Prussian blue film with a thick-
ness of ca. 500 nm is deposited on ITO substrate through cyclic
voltammetry. When a voltage of 20 to 40 V is applied between the
finger and the Prussian blue-coated ITO electrode, fingerprint can
be collected by rolling the fingertip on the electrode. The under-
lying mechanism of this method is that potassium ions in eccrine
sweat transferred to the electrode surface cause electrochromism
of the Prussian blue film. As a consequence, humidity is an im-
portant factor that influence the fingerprint collection. It has been
demonstrated that a relative humidity in the range of 65–80% is
appropriate.
4
Electrochimica Acta 390 (2021) 138798
Bersellini et al. [40] proposed that electropolymerization of pyr-
role and substituted porphyrins could be used for fingerprint de-
velopment. This study is ascribed to the earliest research that fo-
cuses on fingerprint development by electrochemical deposition.
During potential sweep, radical cations generate on superficial nu-
cleation sites through oxidation of monomers near electrode sur-
face, and then react with neutral monomers diffusing to the elec-
trode surface. Polymer films that form on background area lead
to color contrast with fingerprint ridge area. Since electrochromic
properties of the deposited polymer films have not been in-
vestigated, the biggest drawback of this technique is relatively
low contrast. Sapstead et al. [41] reported a new and interest-
ing development strategy based on potentiodynamic polymeriza-
tion of substituted pyrrole ((9H-fluoren-9-yl)methyl-3-(1H-pyrrol-
1-yl)propylcarbamate, PyFMOC). The good leaving group, ester-
bound FMOC, can be hydrolyzed and eluted from poly(PyFMOC)
after deposition, facilitating subsequent amide bonding of Dy-
light 649 NHS ester which is a large fluorophore. This process of
functionalization can introduce fluorescence property into the de-
posited polymer. The effectiveness of this strategy, however, stays
at concept stage and has not been verified by actual test.
3. Fingerprint imaging by ECL
ECL is a kind of chemiluminescence generated during certain
electrochemical reactions by applying a potential. Many chemical
sensors and analytical methods that possess very high sensi-
tivity and selectivity have been established based on ECL. ECL
generated in situ on the reaction interfaces with no need for
external light stimulation shows near-zero background; mean-
while, ECL driven by electrical signal permits accurate spatial
and temporal control throughout the reactions. Therefore, ECL is
extremely suitable for imaging applications such as examining
the functional regions of electrodes and determining the distri-
bution of electrochemical active sites [42]. More recently, many
ECL reaction systems, i.e., [tris(2,2 -bipyridyl)ruthenium(II)]-[tri-n-
propylamine] (Ru(bpy)3 2+ -TPrA), [ruthenium bis(2,2 -bipyridine)
(2,2 -bipyridine-4,4 -dicarboxylic acid) N-hydroxysuccinimide
ester]-[2-(dibutylamino) ethanol] ([Ru(bpy)2 (dcbpy)NHS]2+ -DBAE),
rubrene-TPrA, rebrene-DBAE, luminol-H2 O2 , luminol-K2 S2 O8 ,
polyluminol-H2 O2 and porous silicon (pSi), as listed in Table 2,
have been explored to image latent fingerprints on conductive
substrates [15,43-45]. Spatially selective generation of ECL either
on background area or on fingerprint ridge area can be accom-
plished by utilizing physical, chemical or biological properties
of the fingerprint residues, which makes a significant difference
in luminescence between these two areas and allows sensitive
imaging of latent fingerprints.
3.1. ECL on background area
As was just mentioned in the above section, sebaceous fin-
gerprints on conductive substrates can serve as a mask that
makes underlying area electrochemically inert or less active. Con-
sequently, ECL reactions occur not on fingerprint ridge area, but on
background area, revealing a dark fingerprint pattern on a bright
background. Xu et al. [46] used Ru(bpy)3 2+ -TPrA co-reactant ECL
system in which Ru(bpy)3 2+ acted as the ECL luminophore and
TPrA acted as the co-reactant species to image sebaceous finger-
prints on ITO substrates. As shown in Fig. 2(a)-(c), ECL that visual-
izes the latent fingerprint is generated on background area follow-
ing a well understood mechanism:
Ru(bpy)3 2+ – e → Ru(bpy)3 3+ (4)
TPrA – e → TPrA+ • → TPrA• + H+ (5)
C. Yuan, M. Li, M. Wang et al. Electrochimica Acta 390 (2021) 138798

Table 2
Summary of fingerprint imaging by ECL.

Fingerprint sample / substrate ECL reaction system Applied potential ECL region Refs.

Sebaceous fingerprints / ITO Ru(bpy)3 2+ -TPrA 1.13 V vs. Ag/AgCl Background [46]
Sebaceous fingerprints / stainless steel Ru(bpy)3 2+ -TPrA 1.15 V vs. Ag/AgCl Background [47]
Sebaceous fingerprints / ITO Ru(bpy)3 2+ -TPrA 2.0–3.0 V (voltage) Background [48]
Sebaceous fingerprints / ITO Rubrene-TPrA 2.2 V vs. Ag QRE Background [49]
Sebaceous fingerprints / ITO or stainless steel Luminol-(K2 S2 O8 or H2 O2 ) 1.0 V vs. Ag/AgCl Background [50]
Sebaceous fingerprints / ITO Polyluminol-H2 O2 1.2 V vs. Ag/AgCl Background [51]
Sebaceous fingerprints / pSi Porous 0.8 V vs. Ag/AgCl Background (initial stage) [52]
silicon Fingerprint ridge (final stage)
Sebaceous and eccrine fingerprints / ITO [Ru(bpy)2 (dcbpy)NHS]2+ -DBAE 1.3 V vs. Ag/AgCl Fingerprint ridge [46]
Sebaceous fingerprints / ITO Rubrene-DBAE 2.4 V vs. Ag QRE Fingerprint ridge [49]
Eccrine and natural fingerprints / gold Luminol-H2 O2 −0.7 V vs. Ag/AgCl Fingerprint ridge [53]

Fig. 2. (a) Mechanism of ECL imaging of latent fingerprints on ITO substrates based on the Ru(bpy)3 2+ -TPrA ECL reaction system; (b) bright-field image and (c) ECL image
of a sebaceous fingerprint; (d) schematic diagram of reaction cell and electrodes of the smartphone-based ECL system; (e) ECL, gray and binary fingerprint images under
different exciting potentials. (b) and (c) Reprinted with permission from Ref. [46]. Copyright 2012, John Wiley and Sons. (d-e) Reprinted with permission from Ref. [48].
Copyright 2019, Elsevier B. V.

Ru(bpy)3 3+ + TPrA• → [Ru(bpy)3 2+ ]∗ + products
[Ru(bpy)3 2+ ]∗ → Ru(bpy)3 2+ + hv
Later, this ECL reaction system was studied in detail to im-
age sebaceous fingerprints on stainless steel substrates [47]. A se-
ries of experimental parameters, including applied potential, con-
centration of Ru(bpy)3 2+ and image stability, has been investigated
to optimize the imaging quality. More importantly, sebaceous fin-
gerprints on other non-porous substrates, such as coin, computer
screen, laboratory cabinet and optical disk, have been lifted using
double sided adhesive tape and then released onto stainless steel
substrates. These transferred fingerprints can be visualized by this
ECL system as well. Very recently, by using the Ru(bpy)3 2+ -TPrA
ECL system, Li et al. [48] designed a smartphone-based mobile
testing platform for both fingerprint imaging and in situ biochemi-
cal sensing . USB-based excitation supply and camera-based imag-
ing analysis were integrated in one smartphone by built-in func-
tional modules. ECL imaging measurements have been performed
using a two-electrode system in a 3D printed device as illustrated
in Fig. 2(d). Nicotine with enhancing effect on ECL and trinitro-
toluene (TNT) with quenching effect on ECL as typical exogenous
substances in fingerprint residues have also been analyzed by us-
ing this platform. In addition, as shown in Fig. 2(e), multimode
analysis of ECL images, including color induction, gray-scale pro-
cessing and binary extraction, has been carried out to improve and
enhance the ECL images obtained from fingerprint imaging and
biochemical sensing.
(6) There are some other ECL reaction systems that resemble
Ru(bpy)3 2+ -TPrA ECL system in principle and application of finger-
(7) print imaging. Li et al. [49] proved that rubrene-TPrA ECL system
could be utilized to image sebaceous fingerprints on ITO substrates,
but an organic electrolyte using dimethylformamide (DMF) as the
solvent and a much more positive potential (2.2 V vs. Ag QRE) were
required. Luminol-K2 S2 O8 and luminol-H2 O2 ECL systems were in-
vestigated by Xu et al. [50] for ECL imaging of sebaceous finger-
prints on ITO or stainless steel substrates. Several factors includ-
ing type of co-reactant, applied potential and concentration of ECL
luminophore have been studied to obtain optimized imaging pa-
rameters. However, bubbles may sometimes appear in ECL images
because nitrogen is a reaction product of these two ECL systems.
ECL luminophores in the above-mentioned ECL reaction systems
are dissociated in the electrolytes, which limits the resolution of
fingerprint imaging due to the diffusion of these luminophores.
Furthermore, some reagents such as TPrA in the Ru(bpy)3 2+ -TPrA
ECL system are toxic and harmful to users. To overcome these
disadvantages, inspired by previous studies related to fingerprint
development by electropolymerization, Hu et al. [51] proposed
a new strategy based on polyluminol-H2 O2 ECL system for ECL
imaging of sebaceous fingerprints on ITO substrates. Since the
molecular structure of luminol is similar to aniline, a thin film
of polyluminol can be electrodeposited and formed on the back-
ground area. As a result, the immobilization of ECL luminophores
on the substrate improves imaging resolution, and the use of
H2 O2 as the co-reactant is a safer way for ECL imaging of latent
fingerprints.

5
C. Yuan, M. Li, M. Wang et al. Electrochimica Acta 390 (2021) 138798

Tan et al. [52] proposed a special ECL reaction system based on

pSi for fingerprint imaging. The pSi obtained by anodizing boron-
doped silicon wafer shows anodic ECL that could be initiated by
electron injection from Si-H bonds into the conduction band (CB)
of silicon via surface oxidation, as indicated by the following chem-
ical equation:

Si-H(surface) + H2 O + h+ (VB) → Si-OH(surface) + 2H+ (aq) + e(CB) (8)

The ECL dynamic process of pSi can be perturbed by adsorbed

molecules on its surface. Oil can act as a surface blocker that tem-
porarily prevent the contact between pSi surface and electrolyte,
leading to a retarded activation process. With regard to ECL imag-
ing of sebaceous fingerprints on pSi substrates, the whole ECL pro-
cess on background area, including occurrence, enhancement and
fading, are all expected to happen prior to fingerprint ridge area.
Unlike most current ECL systems, this process does not require any
additional molecular luminophore or co-reactant. Moreover, TNT as
an electron acceptor and tripropylamine as an electron donor show
quenching and enhancing effect on the ECL of pSi, respectively, so
this ECL system provides a way to indicate potential existence of
exogenous substances in fingerprint residues. However, the evalu-
ation results are very preliminary and imprecise, for a great many
chemical substances can influence the ECL dynamic process of pSi.
For instance, p-nitrotoluene, nitrobenzene, and toluene also show
an ECL-quenching effect.

3.2. ECL on fingerprint ridge area

Compared with fingerprint imaging by ECL on background area,

the realization of ECL on fingerprint ridge area is more difficult,
which requires immobilization of ECL luminophores onto finger-
print residues. To achieve this, three different routes based on
physical adsorption, chemical bonding and immune binding have
been developed so far. ECL reactions that occur on fingerprint ridge
Fig. 3. (a) Bright-field image, (b) photoluminescence image and (c) ECL image of
a sebaceous fingerprint after incubation with Ru(bpy)2 (dcbpy)NHS solution for 1 h.
Two possible mechanisms of ECL imaging of latent fingerprints tagged by an ECL
luminophores: (d) completely infiltrated and (e) superficially tagged. (a-c) Reprinted
with permission from Ref. [46]. Copyright 2012, John Wiley and Sons.

area but not on background area reveal a bright fingerprint pattern

on a dark background. Each of these cases will be discussed sep-
trated in Fig. 3(d) and (e). One mechanism is based on the as-
arately in this section. By the way, at the final stage of ECL imag-
sumption that fingerprint residues have been completely infiltrated
ing of sebaceous fingerprints on pSi substrates, ECL also generates
by ECL luminophores. Both ECL luminophores and co-reactants can
only on fingerprint ridge area because of retarded activation of ECL
be oxidized on the surface of working electrode. Then ECL gener-
on this area as well as simultaneous fading of ECL on background
ates from the reaction between Ru(bpy)2 (dcbpy)3+ and DBAD• . The
area, but this relatively impermanent phenomenon is not within
whole process is shown as follows:
the scope of this section.
Li et al. [49] prepared a suspension of rubrene aggregates by
Ru(bpy)2 (dcbpy)2+ (ridge) – e → Ru(bpy)2 (dcbpy)3+ (ridge) (9)
adding water into an ethanol solution of rubrene. When a seba-
ceous fingerprint on ITO substrate is immersed into this suspen-
DBAE(background) – e → DBAE+ • (background)
sion, the dispersed rubrene aggregates that are lipophilic will ad-
→ DBAE• (ridge) + H+ (10)
sorb preferentially on fingerprint residues through hydrophobic in-
teraction. After being transferred to an organic electrolyte contain-
ing acetonitrile as the solvent and DBAE as the co-reactant, the ad- Ru(bpy)2 (dcbpy)3+ (ridge) + DBAE• (ridge)
sorbed rubrene aggregates can react electrochemically with DBAE → [Ru(bpy)2 (dcbpy)2+ ]∗ (ridge) + products (11)
that freely diffuses in the electrolyte under a constant potential
of 2.4 V vs. Ag QRE. To achieve sufficient imaging contrast, this [Ru(bpy)2 (dcbpy)2+ ]∗ (ridge) → Ru(bpy)2 (dcbpy)2+ (ridge) + hv (12)
high potential is essential because the spatial position of ECL lu-
minophores may cause high resistance. The other mechanism is based on the assumption that fin-
A covalent binding of ECL luminophores onto fingerprint gerprint residues have been superficially tagged with ECL lu-
residues was proposed by Xu et al. [46] As amino acids are one minophores. Since these ECL luminophores are far away from
of the main ingredients in eccrine sweat, [Ru(bpy)2 (dcbpy)NHS]2+ the surface of working electrode, only the co-reactants are elec-
as the ECL luminophore can be tagged on fingerprint ridge area trochemically oxidized. Then the free radical DBAE• formed
through the formation of amide bonds, which has been con- by deprotonation of DBAE+ • reduces Ru(bpy)2 (dcbpy)2+ to
firmed by mass spectrometric measurements. To acquire a satis- Ru(bpy)2 (dcbpy)+ . Finally, ECL generates from the reaction be-
fying ECL image, the incubation process requires at least 30 min. tween Ru(bpy)2 (dcbpy)+ and DBAE+ • . These reactions can be ex-
As shown in Fig. 3(a)-(c), the successful imaging of latent finger- pressed as follows:
prints is ascribed to ECL rather than photoluminescence of the lu-
minophores. ECL imaging of latent fingerprints using this ECL sys- DBAE(background) – e → DBAE+ • (background)
tem may follow two possible ECL reaction mechanisms as illus- → DBAE• (ridge) + H+ (13)

6
C. Yuan, M. Li, M. Wang et al.
Fig. 4. ECL images of eccrine fingerprints treated by single-HRP route for the detection of (a) EGF, (b) lysozyme and (c) dermcidin; ECL images of eccrine fingerprints treated
by multiple-HRP route for the detection of (a’) EGF, (b’) lysozyme and (c’) dermcidin. (d) Mechanisms of ECL imaging of latent fingerprints based on enzyme immunoassay.
(a-c’) Reprinted with permission from Ref. [53]. Copyright 2014, The Royal Society of Chemistry.
Ru(bpy)2 (dcbpy)2+ (ridge) + DBAE• (ridge)
→ Ru(bpy)2 (dcbpy)+ (ridge) + products
Ru(bpy)2 (dcbpy)+ (ridge) + DBAE+ • (ridge)
→ [Ru(bpy)2 (dcbpy)2+ ]∗ (ridge) + DBAE
[Ru(bpy)2 (dcbpy)2+ ]∗ (ridge) → Ru(bpy)2 (dcbpy)2+ (ridge) + hv (16)
Through a combination of enzyme-linked immunosensing
methodology and ECL imaging, Xu et al. [53] demonstrated that
highly sensitive and selective imaging of fingerprints on gold sub-
strates could be achieved via detection of specific polypeptide or
protein in fingerprint residues. Since this approach is established
based on immunodetection, it is capable of providing additional
information on specific trace constituents present in fingerprint
residues. Specifically, human immunoglobulin G (hIgG) that is the
main antibody isotype found in blood, and epidermal growth fac-
tor (EGF), lysozyme and dermcidin that present in eccrine sweat
have been selected as the target analytes. Typical ECL images ob-
tained based on this approach are shown in Fig. 4(a)-(c’). General
principle of this method includes two routes of the immunore-
actions that are illustrated in Fig. 4(d), namely single-horseradish
peroxidase (HRP) route and multiple-HRP route. First, the primary
antibodies which are specific for the target analyte are incubated
over the fingerprint on gold substrate. In the single-HRP route, sec-
ondary antibodies that are conjugated with “single” HRP molecule
are used to incubate the sample. In the multiple-HRP route, “mul-
tiple” biotinylated secondary antibodies and HRP-labeled strepta-
vidin are sequentially used to incubated the sample. ECL imaging
is performed by immersing the sample into an electrolyte contain-
ing luminol. A negative potential (−0.7 V vs. Ag/AgCl) that is suf-
ficient to electrochemically reduce the dissolved O2 to H2 O2 is ap-
plied, and then the chemiluminescent oxidation of luminol is cat-
alyzed by the immobilized HRP, visualizing the fingerprint pattern.
Compared with the single-HRP route, more HRP can be labeled on
fingerprint residues using the multiple-HRP route because multi-
ple binding sites are provided by biotinylated antibodies for HRP-
Electrochimica Acta 390 (2021) 138798
labeled streptavidin, resulting in a considerable amplification of the
(14) ECL signal.
4. Fingerprint imaging by scanning probe electrochemistry
(15) techniques
In general, traditional electrochemical techniques measure av-
erage responses over the entire interface between electrode and
electrolyte. The requirement to investigate localized electrochemi-
cal phenomenon results in the emergence of scanning probe elec-
trochemistry techniques that usually integrate a probe for the de-
tection of local information, a positioning system and measure-
ment instruments. In recent years, scanning Kelvin probe (SKP)
and scanning electrochemical microscope (SECM) based on scan-
ning probe electrochemistry techniques with high sensitivity and
high spatial resolution have been used in specific scenarios for fin-
gerprint imaging.
4.1. Fingerprint imaging by SKP
Kelvin probe is a non-contact and non-destructive capacitor de-
vice measuring the relative work function difference between the
probe and a conductive sample. In solid-state physics, work func-
tion describes the minimum energy required to liberate an elec-
tron from the solid surface of a conductor; from an electrochemical
perspective, it is often interpreted as the difference from an elec-
trode’s Fermi level, average energy of electrons, and that of vac-
uum. When a metal microprobe is positioned above the surface a
sample, usually on the order of 100 μm, an energy difference be-
tween their electrons will arise if they are of different metals. Then
the microprobe is electrically shorted with the sample using inte-
rior circuit of the system. As a result, positive charges form on the
surface of one metal while negative charges form on the surface of
the other metal, generating a parallel plate capacitor since a dielec-
tric (air or vacuum) separates the probe and the sample. The probe
is vibrated to periodically change the capacitance, producing an al-
ternating current in external circuit. And then, a “nulling potential”
7
C. Yuan, M. Li, M. Wang et al.
Fig. 5. (a) The principle of fingerprint imaging with a Kelvin probe; (b) schematic diagram of the operation of a Kelvin probe; (c) schematic diagram of scanning a fingerprint
sample with a Kelvin probe; (d) schematic diagram of major components and (e) photograph of a SKP apparatus used for fingerprint imaging. (a-c) Reprinted with permission
from Ref. [54]. Copyright 2018, Elsevier. (e) Reprinted with permission from Ref. [55]. Copyright 2006, Elsevier Ireland Ltd.
is applied and adjusted to minimize this current. The Kelvin probe
measurement is made when the applied voltage causes the current
to become zero.
The principle and apparatus of scanning Kelvin probe used for
fingerprint imaging are presented in Fig. 5. As shown in Fig. 5(a),
Fermi energy level of the surface of a metallic substrate is altered
after fingerprint deposition. As a result, the Volta potential or con-
tact potential difference (CPD) between the probe tip and finger-
print ridge area is different from that between the probe tip and
background area, which can be detected by the Kelvin probe. Tip
diameter determines the spatial resolution of a SKP. An example
of SKP imaging of a latent fingerprint on a 25 × 25 mm metal-
lic substrate using a 100 μm diameter vibrating Kelvin probe is
illustrated in Fig. 5(b) and (c). The probe tip is held at a constant
distance of 100 μm above the sample surface with vibration fre-
quency of 280 Hz and vibration amplitude of 50 μm peak-to-peak,
and then scans in a raster of parallel lines 100 μm apart. The
Kelvin probe measurement is made once after the probe makes
every lateral move of 100 μm, generating a data matrix of Kelvin
probe potential (Ekp ). Typical configuration of a SKP apparatus em-
ployed to image fingerprints on metallic substrates is shown in
Fig. 5(d) and (e).
Williams et al. [56] first demonstrated that latent fingerprints
on metallic substrates including iron, copper and brass could be
imaged using a SKP under ambient conditions. Inorganic salts
present in fingerprint residues induce a depassivation on the metal
surface of fingerprint ridge area, leading to a dramatic decline (typ-
ically larger than 200 mV) in Volta potential compared with back-
ground area. The resultant Volta potential pattern reflecting the
fingerprint topography can be visualized by potential mapping. The
difference in Volta potential may exist for months and can be de-
tected by SKP even when the fingerprint sample is coated by a
polymer layer or heated to a temperature of 600 °C. Soon after-
8
Electrochimica Acta 390 (2021) 138798
wards, more detailed studies have been performed to exploit the
potential of fingerprint imaging by using SKP [55,57,58]. To be spe-
cific, three aspects, i.e., fingerprint characteristics (including chem-
ical composition, and donor gender), external environment (in-
cluding relative humidity, smoke contamination, and physical re-
moval) and non-planar substrates (i.e., cartridge cases), that are
closely associate with fingerprint imaging by SKP have been sys-
temically investigated. As shown in Fig. 6(a) and (b), both seba-
ceous and eccrine fingerprints can be clearly visualized by SKP us-
ing Volta potential mapping, but overall image contrast of seba-
ceous fingerprints is lower due to a presumptive film among their
ridges. Moreover, fingerprint secretions of a proportion of female
donors seem to show a greater degree of local corrosion, giving
rise to a higher Volta potential contrast. As for the external en-
vironment, fingerprint samples exposed to 100% relative humid-
ity are barely visualized by SKP. Nevertheless, fingerprint samples
covered by a soot layer can be visualized, especially for sebaceous
fingerprints. An interesting and valuable finding is that if a nat-
ural fingerprint on metal surface is physically removed, e.g., by
rubbing with a tissue, after it has been deposited for a period
of time (at least 5 min for iron surface and 1 h for brass sur-
face), it can still be detected and imaged by SKP. Except for pla-
nar metallic substrates, SKP is also capable of imaging latent fin-
gerprints on non-planar metallic substrates by performing a pre-
liminary height scan in a topography mode to maintain a constant
probe-to-sample distance. A Volta potential pattern of an eccrine
fingerprint deposited on a cartridge case post-firing is shown in
Fig. 6(c). In practical terms, however, detection and imaging of fin-
gerprints on fired cartridge cases that have been deposited pre-
firing is more meaningful and challenging, for fingerprints may be
badly damaged by heat and friction. The recovery rate of such fin-
gerprints on relatively unaffected area using SKP imaging is around
80%.
C. Yuan, M. Li, M. Wang et al.
Fig. 6. Volta potential patterns of (a) sebaceous and (b) eccrine fingerprints deposited on iron substrates as imaged by a SKP; (c) photograph indicating SKP scanning region
and corresponding Volta potential pattern obtained for a 0.45 in. caliber cartridge case bearing an eccrine fingerprint deposited post-firing; (d) optical image of a fingerprint
on brass treated by Au-Zn VMD on left side; (e) SKP image of the region of the black border in (d); (f) CPD contrast between fingerprint ridges for i to ii and iii to iv as
labeled in (e). (a-c) Reprinted with permission from Ref. [55]. Copyright 2006, Elsevier Ireland Ltd. (d-f) Reprinted with permission form Ref. [54]. Copyright 2018, Elsevier.
Dafydd et al. [59] investigated the application of vacuum metal
deposition (VMD) before SKP imaging of fingerprints on metallic
substrates. VMD is an established method for the development of
latent fingerprints on non-porous substrates. It was initially intro-
duced by Theys et al. [60] in the late 1960s and was first used
operationally by Kent et al. [61] in the mid-1970s. The most com-
mon VMD method involves evaporation and deposition of gold fol-
lowed by zinc under vacuum. Under normal conditions, gold de-
posited on fingerprint ridge area is buried at certain depth in fin-
gerprint residues, so subsequent zinc only deposits on background
area where the deposited gold is exposed, leading to the devel-
opment of a “negative” fingerprint. Except for gold-zinc combina-
tion for fingerprint development, the use of gold or silver VMD are
also well established for operational work. Since SKP is a poten-
tiometric apparatus, the best imaging contrast is obtained when
the potentials between fingerprint ridge area and background area
differ most. This can be achieved by selecting appropriate depo-
sition metals to create a large potential difference between these
two areas. It is found that gold-zinc VMD for noble metallic sub-
strates and silver VMD for non-noble metallic substrates work well
in most cases. Some results obtained by Challinger et al., [54] as
shown in Fig. 6(d)-(f), prove the improvement in SKP imaging af-
ter VMD treatment, but mixed results are observed in other cases.
Also, in this research, SKP as a fingerprint imaging method deal-
ing with metallic substrates is compared with SEM, electron probe
micro-analyzer (EPMA) and cathodoluminescence techniques. Un-
like SKP measurements that can be performed under ambient con-
ditions, these techniques need a vacuum and high-energy electron
bombardment which may influence subsequent forensic analysis.
Besides, using a 1 mm tip gives the possibility of rapidly inspect-
ing a large area, which is suitable for initial analysis to identify the
location of a fingerprint.
4.2. Fingerprint imaging by SECM
SECM is another type of scanning probe electrochemistry tech-
nique for measuring localized electrochemical behavior of various
liquid/solid, liquid/gas and liquid/liquid interfaces. Some key ap-
plications of SECM include mapping of sample topography, deter-
9
Electrochimica Acta 390 (2021) 138798
mination of local electrochemical reactivity, and micro-fabrication.
Typical SECM apparatus, as illustrated in Fig. 7(a) and (b), in-
tegrates an ultromicroelectrode (UME) probe, a positioning sys-
tem for movement and control of the probe, and a bipotentiostat
for polarization of electrode(s) and measurement of resulting cur-
rent(s). [62] Standard UME probes used in SECM, as illustrated in
Fig. 7(c), are usually rigid and made of a noble metal wire (e.g., Pt
wire) imbedded in a glass sheath. They are specially designed to
have an active radius (the radius of the wire, a) below 100 μm and
a specific tapered polish (per the RG ratio, RG = rg /a, where rg is
the radius of the sheath). Feedback mode and generator-collector
mode are two predominant operation modes of SECM. The prin-
ciple of the feedback mode is illustrated in Fig. 7(d). A DC volt-
age is applied to the probe as it is incremented towards the sam-
ple, while the DC current response is collected. In bulk solution,
a steady-state current limited by hemispherical diffusion is pro-
duced at the tip. When the distance in z-direction between the
tip and the sample is about 2–4 times that of the probe diame-
ter, the current response at the tip changes from a bulk response
to a local response. Over an area of high conductivity, a local cur-
rent enhanced over the bulk value is detected due to a Nernstian
response (positive feedback effect). However, over a region of low
conductivity, local current is decreased relative to the bulk cur-
rent because mass-transport is hindered to the probe (negative
feedback effect). Eventually, a data map of local current is cre-
ated by scanning the probe using a raster pattern just like the SKP
scanning, and charting the position with collected electrochemical
parameters.
A series of previous studies as listed in Table 3 have shown
that the feedback mode of SECM is an effective electrochemical
means for imaging both labeled and label-free fingerprints, for the
local response current at fingerprint ridge area is significantly dif-
ferent from that at background area in these cases. Labeled finger-
prints herein refer to fingerprint samples that have been treated
with certain development or enhancement process prior to SECM
imaging, including silver staining, multimetal deposition (MMD),
benzoquinone tagging, VMD and cyanoacrylate fuming. Label ef-
fect may act on either fingerprint ridge area or background area
as long as the resulting difference in electrochemical characteris-
C. Yuan, M. Li, M. Wang et al. Electrochimica Acta 390 (2021) 138798

Fig. 7. (a) Schematic diagram of the major components of a SECM apparatus; (b) structural diagram of a SECM apparatus; (c) schematic diagram of the structure of an
ultramicroelectrode; (d) schematic diagram of the feedback mode of SECM.

Table 3
Summary of fingerprint imaging using the feedback mode of SECM.

Fingerprint sample / substrate Probe Redox mediator Probe potential Refs.

Silver-stained protein fingerprints / PVDF Pt disk UME K3 IrCl6 0.8 V vs. Ag QRE [63]
MMD-enhanced fingerprints / glass Pt disk UME K3 IrCl6 0.8 V vs. Ag QRE [64]
Benzoquinone-tagged protein fingerprints / PVDF Pt disk UME K3 Fe(CN)6 −0.2 V vs. Ag QRE [65]
VMD-enhanced fingerprints / glass Pt disk UME FcMeOH 0.3 V vs. Ag QRE [66]
Cyanoacrylate-fumed fingerprints / gold Push-pull UME FcMeOH 0.4 V vs. Ag/AgCl QRE [67]
Sebaceous fingerprints / five types of metals Pt disk UME FcMeOH 0.3 V vs. Ag QRE [68]
Not specified fingerprints / ITO Pt disk UME K3 Fe(CN)6 0.1 V vs. Ag/AgCl QRE [69]
Blood fingerprints / PVDF Pt disk UME [Ru(NH3 )6 ]Cl3 −0.4 V vs. Ag QRE [70]
Sebaceous and natural fingerprints / nitrocellulose Pt disk UME Methyl viologen −0.85 V vs. Ag QRE [71]

tics between these two areas can be detected by SECM. Accord-
ingly, label-free fingerprints refer to fingerprint samples submitted
directly to SECM imaging as deposited without treatment.
4.2.1. SECM imaging of labeled fingerprints
Silver staining, initially introduced by Switzer et al. in 1979,
[72] is a sensitive method for detecting proteins. The mechanism
of silver staining depends on the binding of silver ions to -COOH
and -SH groups of proteins, and then the reduction to insoluble
silver nanoparticles. This process is autocatalytic and finally al-
lows protein bands to become visible. It has been proven that
silver-stained proteins on PVDF membranes can be visualized by
using the feedback mode of SECM [73]. Shortly afterwards, this
methodology was extended by Zhang et al. [63] to image silver-
stained protein fingerprints on PVDF membranes. As illustrated in
Fig. 8(a), a Pt disk UME served as the SECM probe is kept at a
high enough potential (0.8 V vs. Ag QRE) to oxidize the media-
tor IrCl6 3− in electrolyte solution. Approach curve is employed to
determine an appropriate working distance between the tip and
the sample. Resultant Faradaic current is collected as the signal
for fingerprint imaging. When the probe scans over the fingerprint
ridge area, local response current increases (positive feedback ef-
fect) because the oxidation product IrCl6 2− can be reduced back to
IrCl6 3− through a heterogeneous electron transfer reaction with sil-
ver nanoparticles. By contrast, when the probe is positioned above
the background area, the diffusion of IrCl6 3− to the tip is hindered,
resulting in a decrease in local response current (negative feed-
back effect). That is, there is an obvious difference in electrochem-
ical reactivity between fingerprint ridge area and background area.
Based on the local response current and corresponding tip coordi-
nate during point-by-point planar scanning, the image in Fig. 8(b)
showing part of a silver-stained protein fingerprint is obtained. Be-
sides, fingerprints developed by MMD are very similar in chem-
ical properties compared with those developed by silver staining
because metallic silver layer exists on the surface of fingerprint
ridge area. MMD, originally introduced by Saunders in 1989, [74] is
considered a versatile method for developing latent fingerprints
on porous, semi-porous and non-porous substrates. MMD usually
consists of two successive steps of staining using colloidal gold
and silver developer, respectively. In the first step, gold nanopar-
ticles form and electrostatically adsorb on certain macromolecular
components (e.g., lipids, proteins, peptides) of fingerprint residues.
Then in the latter step, metallic silver preferentially deposits on
the gold nanoparticles, amplifying gold staining and enhancing the
visibility of the fingerprint. Using the same electrochemical system
and similar imaging parameters, Zhang et al. [64] have demon-
strated that SECM can be employed to acquire high-resolution im-
ages of MMD-enhanced fingerprints.
Protein fingerprints containing cysteines with free -SH groups
can be tagged with benzoquinone through a 1,4-Michael addi-

10
C. Yuan, M. Li, M. Wang et al. Electrochimica Acta 390 (2021) 138798

Fig. 8. (a) Schematic diagram of SECM imaging of silver-stained fingerprints; (b) SECM image of a silver-stained fingerprint on PVDF membrane; (c) schematic diagram of the
operation of a push-pull probe; (d) SECM image of a fingerprint (artificially contaminated with picric acid and then developed by cyanoacrylate fuming) on gold substrate;
(e) schematic diagram of SECM imaging of fingerprints with the push-pull probe; (f) MALDI-MS spectra of collected liquid portions. (b) Reprinted with permission from Ref.
[63]. Copyright 2007, Elsevier B. V. (c-f) Reprinted with permission from Ref. [67]. Copyright 2012, American Chemical Society.

tion reaction, usually producing a mixture of hydroquinone- and
benzoquinone-protein adducts. The product composition depends
on the amount of benzoquinone because hydroquinone-protein
adducts will be oxidized to benzoquinone-protein adducts if ex-
cess benzoquinone is added. On this basis, two possible strate-
gies for SECM imaging of benzoquinone-tagged protein fingerprints
were proposed by Cortés-Salazar et al. [65] In the first strat-
egy, benzoquinone-protein adducts in fingerprint residues are com-
pletely reduced by a Sn(II) solution, which can be imaged by using
the IrCl6 3− system as described above, but this route is not prac-
tical since hydroquinone species are easily re-oxidized by oxygen
in air. The second strategy deals with fingerprints tagged by excess
benzoquinone and relies on the diffusion-controlled reduction of
mediator Fe(CN)6 3− . Positive feedback is developed at fingerprint
ridge area due to recycling of Fe(CN)6 4− through reacting with
benzoquinone species, while negative feedback is encountered at
background area. Although experimental evidence suggests that
the sensitivity of benzoquinone tagging is lower than that of sil-
ver staining, the third level of fingerprints labeled by these two
methods are well presented by SECM imaging. However, a draw-
back of silver staining and benzoquinone tagging is that they are
not applicable to label proteins on conductive surfaces. More de-
tailed information about SECM imaging of fingerprints labeled by
silver staining, MMD and benzoquinone tagging is provided in a
few reviews or feature articles [75-77].
Zhang et al. [66] described a simplified VMD method based
on one-step deposition of Al-doped ZnO film by direct current
magnetron sputtering, which could serve not only as a finger-
print development method, but also as a label process for high-
resolution SECM imaging. It should be noted here that the la-
bel effect acts only on the background area, leading to the for-
mation of insulating fingerprint ridge area and conductive back-
ground area. When a constant potential of 0.3 V vs. Ag QRE is
applied to the tip to oxidize the mediator FcMeOH, conductive
background area covered with Al-doped ZnO film generates posi-
tive feedback due to the reduction of FcMeOH+ back to FcMeOH,
while insulating fingerprint ridge area generates negative feedback,
which reflect the topography of the fingerprint. SECM imaging af-
ter VMD development can be helpful to eliminate the interfer-
ence induced by background color of the substrate. Another inter-
esting research performed by Momotenko et al. [67] successfully
integrated a SECM equipped with a microfluidic push-pull probe
with a matrix-assisted laser desorption/ionization mass spectrom-
etry (MALDI-MS). As shown in Fig. 8(c)-(f), simultaneous SECM
imaging of cyanoacrylate-fumed fingerprint on gold substrate and
MALDI analysis of picric acid artificially left in fingerprint residues
as an explosive contaminant have been demonstrated in this study.
Cyanoacrylate fuming, discovered in the late 1970s, is one of the
most frequently used method for developing latent fingerprints
on non-porous and semi-porous substrates. Fingerprint residues
can initiate the polymerization of cyanoacrylate fumes, forming a
three-dimensional polycyanoacrylate thin film on fingerprint ridge
area that can be infiltrated by electrolyte droplet. Electrochemi-
cal reactivity of cyanoacrylate-fumed fingerprints is similar to that
of VMD-enhanced fingerprints, so the SECM feedback mode as il-
lustrated in Fig. 8(e) resembles that employed for SECM imaging
of VMD-enhanced fingerprints. In addition, liquid portions gath-
ered from the scanned fingerprint have been analyzed by MALDI.
The result in Fig. 8(f) indicates that it is possible to detect down
to 28.5 nmol of picric acid deposited on human finger, showing
the compatibility between SECM imaging and chemical analysis of
trace evidence.

11
C. Yuan, M. Li, M. Wang et al. Electrochimica Acta 390 (2021) 138798

4.2.2. SECM imaging of label-free fingerprints

It is not difficult to reach a conclusion that latent fingerprints
formed by deposition of insulating fingerprint residues on con-
ductive substrates, especially various metallic substrates, have sim-
ilar spatial distribution of electrical conductivity compared with
the above-mentioned VMD-enhanced fingerprints on glass sub-
strates and cyanoacrylate-fumed fingerprints on gold substrates.
So, in theory, the same electrochemical system using FcMeOH as
the redox mediator can be utilized for imaging such fingerprints
by SECM. A research performed by Qin et al. [68] demonstrates
that SECM imaging of sebaceous fingerprints on gold, platinum,
silver, copper and stainless steel surfaces can acquire more mor-
phological information compared with optical microscope imaging.
For example, it is observed from the grayscale SECM images that
there are more residues on the edges than the inner regions of
fingerprint ridges, which is caused by different pressure distribu-
tion across the ridges when pressing the finger onto the substrate.
The resolution of SECM imaging is very important for its applica-
tion in fingerprint imaging, but redox reaction on the tip is a diffu-
sion process that will be affected by probe movement, resulting in
blurred images. To improve the clarity and resolution of SECM im-
age, Wang et al. [69] proposed a digital image processing method
that combined LoG algorithm with new edge-directed interpola-
tion algorithm. SECM imaging of a fingerprint on ITO substrate has
been processed using this method. Improved image contrast and
sharpened fingerprint ridges verify its effectiveness.
Blood fingerprints refer to fingerprints deposited on nearly Fig. 9. (a) Schematic diagram of an electrochemical current imaging technique
dried bloodstains or formed by transfer of blood from blood- based on PECM; (b) electrochemical current image of a fingerprint on a gold sub-
contaminated friction ridge skin to substrate surface. They are one strate at −0.28 V vs. Ag/AgCl; (c) schematic diagram of the three-electrode cell used
for EIS measurements. (a-b) Reprinted with permission from Ref. [82]. Copyright
of the most important fingerprint evidences as they appear very
2010, American Association for the Advancement of Science. (c) Reprinted with per-
frequently at violent crime scenes. Many blood fingerprints are mission from Ref. [83]. Copyright 2017, Elsevier B. V.
visible to the naked eye on account of the characteristic color of
blood. However, if the amount of transferred blood is too small,
there may also be some less visible or latent blood fingerprints can be momentarily developed by water, although it is merely a
that need enhancement or development before photography. Tra- physical process that has no relation to electrochemical effect.
ditional methods of dealing with blood fingerprints rely on chemi-
cal reagents including heme sensitive compounds, amino acid sen- 5. Fingerprint analysis using other electrochemical techniques
sitive compounds, and dyes for protein staining, which are con-
sidered destructive. Using [Ru(NH3 )6 ]Cl3 as the redox mediator, Surface plasmon resonance (SPR) is the collective oscillation of
Tian et al. [70] proposed a label-free strategy for SECM imaging conduction-band electrons at the interface between a metal and
of blood fingerprints on PVDF membranes. [Ru(NH3 )6 ]2+ produced a dielectric, which is excited by light of an appropriate wave-
by the reduction of [Ru(NH3 )6 ]3+ at a tip potential of −0.4 V vs. length and angle (resonant angle) [78]. Both non-Faradaic process
Ag QRE can be re-oxidized by hemichrome present in blood fin- and Faradaic process that occur in electrochemical reactions can
gerprint residues, but this recycling process cannot occur in back- change the refractive index of electrolyte near the electrode sur-
ground area. This highly sensitive approach is effective even for face, leading to the change of output SPR signal [79]. Therefore,
blood fingerprints deposited with 10 0 0-fold diluted blood which many studies have been performed to combine electrochemistry
are difficult to discern under optical microscopy. Moreover, com- with SPR, namely electrochemical surface plasmon resonance [80].
mercially available PVDF membranes have been used to lift blood Plasmonics-based electrochemical current microscopy (PECM), de-
fingerprints on common substrates including glass and banknote. rived from surface plasmon resonance microscopy, is able to image
Lifted fingerprints can be efficiently imaged by this method as well. local electrochemical current with a high spatial resolution that is
Shi et al. [71] proposed another label-free strategy for SECM close to optical diffraction limit. As shown in Fig. 9(a), the basic
imaging of sebaceous and natural fingerprints on nitrocellulose principle of PECM relies on the derivation of local current from SPR
membranes using methyl viologen (MV2+ ) as the redox mediator. images of the working electrode surface captured consecutively
MV2+ is reduced to MV+ when a constant potential of −0.85 V during the electrochemical process [81]. A quantitative model for
vs. Ag QRE is applied to the probe. As the probe approaches to- the conversion of SPR signals to current has been established by
wards fingerprint ridge area, MV+ reacts with adsorbed electroac- Shan et al. [82] in a milestone study. As shown in Fig. 9(b), a fin-
tive species in fingerprint residues to produce MV2+ , generating a gerprint on gold substrate can be revealed by the electrochemi-
positive feedback. Background area hinders the diffusion of MV2+ , cal current images. This technique can also be used to detect trace
causing a negative feedback. There is evidence that squalene, a chemicals, such as traces of TNT in fingerprint residues.
main constituent of sebaceous secretions, contributes the intrin- Determination of fingerprint age is of great significance in the
sic electrochemical reactivity for this label-free SECM imaging. Fur- field of forensic science since it would allow recognition of fin-
thermore, latent fingerprints on various substrates, such as glass, gerprints that are closely related to criminal activities. In fact,
ceramic cup, human skin and leather, can be lifted by nitrocellu- the aging of fingerprints is a very complicated process, which
lose membranes and then imaged using this approach, greatly ex- is affected by several factors including chemical composition of
panding the scope of application. By the way, an interesting phe- fingerprint residues, nature of the substrates and environmen-
nomenon is that latent fingerprints on nitrocellulose membranes tal aspects. Hence, fingerprint age determination is still a grand

12
C. Yuan, M. Li, M. Wang et al.
challenge because of the lack of responsible approaches. Electro-
chemical impedance spectroscopy (EIS) was utilized by Rosa et al.
[83] to monitor and quantify the physical changes in fingerprints
deposited on metallic substrates. The configuration of the specially
designed electrochemical cell used for EIS measurements is pre-
sented in Fig. 9(c). This study allows a deeper understanding of
the aging mechanism of fingerprints on metallic substrates.
6. Conclusion and outlook
In this review article, we have summarized recent progress in
the development and imaging of latent fingerprints based on var-
ious electrochemical techniques. Specifically, we focus on the as-
pects of fundamentals and applications. Various electrochemical
deposition systems performed using different deposition protocols
including anodic deposition, cathodic deposition and cyclic voltam-
metric deposition are very suitable to develop latent fingerprints
that are deposited on metallic substrates and rich in lipids. Many
electrochemical deposition systems have also been proven effective
in developing eccrine fingerprints, although eccrine sweat is tradi-
tionally supposed to dissolve in aqueous electrolytes. Furthermore,
fingerprints developed by some deposits such as polyaniline, PE-
DOT and Co3 O4 can be further enhanced by utilizing their elec-
trochromic properties. Through spatially and temporally control-
ling ECL reactions, luminescence can occur either on fingerprint
ridge area or on background area, resulting in rapid and sensitive
imaging of latent fingerprints. However, some fingerprint imaging
systems based on ECL require clean samples or unconventional
electrodes and are difficult to apply. SKP and SECM, as two typ-
ical scanning probe electrochemistry techniques, have been em-
ployed as non-contact and non-destructive methods for fingerprint
imaging and enhancement. And theoretically, their imaging and
enhancement process does not interfere with subsequent forensic
analysis, but the main challenge for them is relatively low imaging
speed. Besides the above electrochemical techniques, PECM and EIS
have also been explored for fingerprint analysis.
A more comprehensive analysis is conducted to reveal the ad-
vantages and disadvantages of the methods described in this re-
view. As we know, when selecting a method to develop or im-
age a fingerprint, the properties of both substrate and fingerprint
residues have to be considered. Overall, it can be concluded that
these electrochemical methods can only deal with fingerprints on
non-porous substrates, with only one exception—ECL imaging of
fingerprints on pSi substrates which belong to porous substrates.
To be more specific, fingerprint development and imaging meth-
ods based on electrochemical deposition and ECL require the sub-
strates to be conductive; substrates in fingerprint imaging by SKP
are typically restricted to metals. Besides, since anodic deposition,
cyclic voltammetric deposition and some ECL systems involve elec-
trochemical oxidation process at relatively high electrode potential,
most substrates composed of active metals are not applicable. The
cost and time needed to develop or image fingerprints are very
important parameters because they are vital to the flexibility and
usability of a newly established method. Since fingerprint imaging
by scanning probe electrochemistry techniques including SKP and
SECM requires expensive equipment, its cost is much higher than
other electrochemical fingerprint development and imaging meth-
ods that usually use electrochemical workstation as the control and
measurement equipment. Although the amount of time spent per-
forming a development or imaging experiment varies depending
on the specific technical route used, generally, fingerprint devel-
opment by electrochemical deposition and fingerprint imaging by
ECL take similar length of time when compared with most con-
ventional methods, while imaging of a whole fingerprint by using
SKP or SECM may take several hours or even days. Limited by the
configuration of electrochemical cell which directly influences the
13
Electrochimica Acta 390 (2021) 138798
effective area of working electrode, it is difficult to scale up elec-
trochemical development and imaging methods for large area. This
disadvantage becomes especially evident when performing finger-
print imaging by scanning probe electrochemistry techniques due
to the use of microelectrode, though employing multi-electrode
probes and relatively high scan rates could be partial solutions.
So far, lots of progress has been made on electrochemical devel-
opment and imaging of latent fingerprints, but there are still many
aspects that need to be resolved. First, most introduced electro-
chemical methods are able to reveal the three levels of features of
latent fingerprints; meanwhile, a few studies including electrode-
position of polymers and SKP imaging show excellent sensitivity
and frequently outperform many traditional methods. It is also im-
pressive that, in a few cases, the combination of electrochemical
methods and other analytical techniques can provide both mor-
phological information of fingerprints and biochemical information
of fingerprint residues. However, there is still a lack of system-
atic analysis concerning these topics. Furthermore, electrochemical
methods are supposed to have little impact on forensic analysis of
fingerprint residues; nevertheless, a very limited number of con-
firmatory tests have been performed so far. Finally, practical ap-
plication of these emerging methods is still at the early stage and
should be further promoted.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared to
influence the work reported in this paper.
Acknowledgements
This work is financially supported by the National Natural Sci-
ence Foundation of China (21802169); the Scientific Research Foun-
dation for Doctors from Liaoning Province (20170520204); and the
Scientific Research Foundation for Doctors from Criminal Investiga-
tion Police University of China (D2017018).
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