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 ECS Sensors Plus, 2022 1 010602

Editors’ Choice—Review—3D Printing: An Innovative Trend in

Analytical Sensing
Dalton L. Glasco,∗ Anjaiah Sheelam,∗ Nguyen H. B. Ho, Art Matthew Mamaril,
Melissa King, and Jeffrey G. Bell∗,z
Department of Chemistry, Washington State University, Pullman—99164, Washington, United States of America

The rise of additive manufacturing (i.e., 3D printing) as a key technology to rapidly fabricate materials with high quality and
modifiable functionality is playing a major role in many scientific disciplines. Aided by advances in printer capabilities (e.g.,
resolution, material compatibility, print speed, etc) and the availability of affordable low-profile printers, 3D printing is rapidly
becoming a staple piece of equipment in many chemistry research laboratories. One such area that 3D printing is having a profound
impact is on analytical chemistry through the ability to rapidly print and prototype diagnostic devices for use in fields ranging from
the environment to human health. This review describes recent advances in the fabrication of analytical devices which incorporate
3D printed sensing elements into electrochemical or physical sensors. Here we present an overview of the key milestones which
have shaped the current state-of-the-art 3D printers as well as review progress made toward the development of sensors and their
translation (and incorporation) into point-of-care devices such as wearables and soft robots.
© 2022 The Author(s). Published on behalf of The Electrochemical Society by IOP Publishing Limited. This is an open access
article distributed under the terms of the Creative Commons Attribution 4.0 License (CC BY, http://creativecommons.org/licenses/
by/4.0/), which permits unrestricted reuse of the work in any medium, provided the original work is properly cited. [DOI: 10.1149/
2754-2726/ac5c7a]

Manuscript submitted February 18, 2022; revised manuscript received March 9, 2022. Published April 7, 2022.

Society finds itself at a point where the collection, analysis and
interpretation of data is of paramount importance. As such, there is a
concerted effort to exploit the newest technologies towards data
collection through the development of diverse and robust sensors1–4
that collect various chemical,5–7 biological,8–10 and physical11–13
information. Of particular interest are sensors and/or devices which
are deployable at the point-of-use (POU)14–16 or point-of-care
(POC).17–20 A breakthrough in POC sensing came in the 2000s
from the Whitesides group,21 through their use of paper as the
substrate for the sensor’s functional components. Being mass-
produced, the use of paper in constructing analytical devices allowed
for the development of sensors which are (i) low-cost, (ii) capable of
storing and transporting chemical reagents, and (iii) easily disposed
of through incineration (important when analyzing biological
samples).22–25 While many analytical techniques have successfully
been implemented at the POC,26–28 electrochemical approaches
(e.g., amperometric,29,30 potentiometric,31–33 voltammetric,34–36
etc) have been used more frequently owing to their sensitivity,
reliability, and their ability to be miniaturized and integrated with
electronics.37 Furthermore, recent advances in the development of
low-cost and miniaturized potentiostats have allowed researchers to
entirely leave the laboratory setting to perform measurements.38–41
Coupling the rise of portable potentiostats with powerful smart-
phones has drastically altered the traditional landscape of healthcare,
by allowing for decentralized diagnostics through the instantaneous
transmission of data (i.e., diagnostic results) from the field to the
appropriate healthcare practitioner. While we now have at our
disposal the tools to perform measurements reliably outside of the
traditional laboratory setting, the process of fabricating sensors is
currently experiencing a revolution owing to the emerging tech-
nology of 3D printing.42–44
3D printing is an additive manufacturing technique where many
types of materials are used to build structures,45–47 scaffolds,48–50
and even sensors.51–53 3D printing is a generalized term for the many
different techniques used to additively produce these designs.54 For
most 3D printing techniques, a design is produced using computer
aided design (CAD) software. A standard tessellation language (.stl)
file is used to transfer the design to the corresponding 3D printing (or
slicing) software. Slicing software is used to cut a 3-dimensional
design into appropriate thickness layers for the 3D printer to create
∗
Electrochemical Society Member.
z
E-mail: Jeffrey.g.bell@wsu.edu
the design.55–57 Once the design is sliced, the 3D printer fabricates
the design according to the desired spatial dimensions. With its
inherent versatility, it should be no surprise that 3D printing has
begun to permeate academic research, making profound impacts in
fields which are taking advantage of the ability to rapidly prototype
and iterate devices.58,59
In this review, we focus primarily on the application of 3D
printing towards the fabrication of the active sensing element used in
the development of physical and electrochemical sensors. Here we
have summarized and discussed the different approaches and
applications researchers have used towards 3D printing sensors
composed of various materials. Electrochemical sensors which use
3D printed material directly, or after a modification step, to perform
an analytical measurement are receiving substantial attention.
Interesting examples of 3D printed physical sensors for various
applications and their role in increasing the functionality of soft
robots is discussed in relation to their in-field applications. Although
sensor components such as housings, microfluidics, conductive
traces, etc, have been 3D printed, they are outside the primary
scope of this review and will only briefly be discussed. Lastly,
innovations in the field of energy storage are discussed as it pertains
to the 3D printing of anodes and/or cathodes. While our aim in this
review is to give a thorough treatment on the progress and
application of 3D printing towards the development of electroche-
mical and physical sensors, we direct readers to other outstanding
reviews which specifically focus on the different types of 3D
printing: i) stereolithography,55 ii) fused-deposition modeling,56
and iii) selective laser sintering.57 We also direct the readers to
interesting reviews related to the role of 3D printing in energy
storage/conversion applications.60,61
Key Milestones in the Development of 3D Printing Technology
Solid-freeform technology, (i.e., additive manufacturing) is
popularly known as 3D printing. 3D printing is a “bottom-up”
fabrication method which produces structures with defined shape via
layer-by-layer deposition and curing. In the early 1980s at the
University of Colorado, Charles W. Hull, who was motivated by
imperfections in product design, began the laborious task of
developing a new technology which would mitigate such
imperfections.62 In 1986, he patented his first invention on the
technique of stereolithography. Hull developed a.stl file format for
use in CAD software to transfer it to anywhere in the world through
the internet. Hull also developed the first 3D printer, the stereo-
lithography apparatus, and introduced the first commercially
 ECS Sensors Plus, 2022 1 010602

Figure 1. Timeline illustrating some of the important milestones relating to 3D printing technology and its application in the fabrication of sensors.

available 3D printer, the SLA-250. The first printed 3D object was a

small black-eye wash cup using stereolithography.
In 1992, Scott Crump patented another important and more
affordable technique in 3D printing called fused-deposition mod-
eling (FDM).63 Soon after in 1993, Michael Cima and Emanuel
Sachs, from Massachusetts Institute of Technology patented a
machine named “3D printer,” which could print metal, plastic, and
ceramic materials.64 The interest in, and development of 3D printers
was amplified with the emergence of several companies such as
DTM corporation, Z corporation, solidscape and object geometries.
Remarkably, companies such as Organovo and Helisys can print
objects composed of living human tissue,65,66 whereas other
industrial sectors such as the aerospace and automotive industries,
have used 3D printing to prototype aircraft and automotive parts.67,68
Governmental agencies have also exploited 3D printing technology
to rapidly print, and manufacture firearms and it was in the early
2000s when dental implants and prosthetics were fabricated,69,70 that
3D printing was introduced to the medical device field. Owing to its
fast prototyping, inexpensive, and flexible design capability, 3D
printing became extremely popular in electrochemical energy
storage and conversion.71 For example, in 2015 Arenas et al. utilized
3D printing to define electrolyte flow channels and fabricated a
redox flow battery.72 The first glucose dehydrogenase biosensor was
fabricated by Adams et al. in 2018, which was reported to show a
linear detection between 0–400 mg dL−1 of glucose.73 In 2020,
using a dual-extruder 3D printer, the Kokkinos group fabricated an
electrochemical cell-on-a-chip in a single-step process.74 An inter-
esting advancement occurred in 2020, when Joao et al. introduced a
3D printing pen capable of printing a biodegradable carbon black/
polylactic acid (PLA)-based filament, which was used for on-site
detection of Pb and Cu ions in aqueous and hydroethanolic media.75
Figure 1 highlights some of the significant advancements in the
development of 3D printing technology as well as its application in
the field of analytical sensing.
A search in the Web of Science database using the keyword “3D
printing,” shows approximately 54300 research articles (including
2600 review articles) have been published to date. The number of
publications/reviews vs year is shown in Figs. 2a and 2b. It can be
observed from these figures that a steep increase in publications Figure 2. The exponential growth rate of publications on 3D printing. (a)
began in 2014. This data indicates the use of 3D printing in various Research articles and (b) reviews. (Source: Web of Science, keyword: “3D
applications, including electrochemical sensing, physical sensing, Printing” in topic.)
energy storage and application, food industry, automotive, military,
and other industries. which are built into a desired pattern or design. FDM is a filament-
based technique where diverse materials such as acrylonitrile
Types of 3D Printing butadiene styrene (ABS),77 polylactic acid (PLA),78 polystyrene,79
Fused-deposition modelling.—Fused deposition modeling polycarbonates,80 polyethylene terephthalate (PET),81 polyvinyl
(FDM) is one of the major commercial versions of 3D printing.76 alcohol (PVA),82 polyamide (i.e., Nylon),83 polycaprolactone
This technique uses extruded material to form layered structures (PCL),84 polybutylene terephthalate (PBT),85 and polyglycolic acid
Table I. Comparison of several 3D printing styles used in analytical chemistry.

ECS Sensors Plus, 2022 1 010602

Resolution
Method Materials Benefits Drawbacks Cost range

FDM, Thermoplastic filament, Conductive filament, nanoparticle Low cost, high Mechanical strength, Limited $200–$1500 50–200 μm
FFF infused filament, fiber-reinforced filament, speed, simplicity material (thermoplastics)
SLA, Photocurable monomer resins, hybrid polymer-ceramics Fine resolution, Very limited materials, slow $400–$5000 10–100 μm
DLP high quality printing, partly expensive
SLS, Metallic powders, alloys, limited polymers, ceramics, Fine resolution, Slow printing, expensive, high $10,000–$175,000 80–250 μm
SLM high quality porosity in binding method

FFF—Fused filament fabrication, SLM—Selective laser melting.

 ECS Sensors Plus, 2022 1 010602
Figure 3. (a) Schematic representation of the 3D printing fabrication for a
single-step cell-on-a-chip device using a dual extruder FDM printer. (b)
CAD dimensions of the 3D printed device (cm). (c) Comparison photograph
of the 3D printed device to a coin. Reproduced from V. Katseli, A.
Economou, and C. Kikkinos, Talanta, 208, 120388 (2020). Copyright
2022 with permission from Elsevier.
(PGA)86 can be printed owing to their inertness (i.e., no chemical
reactions occur) in the fabrication process. Conductive thermoplas-
tics have also become commercially available providing a unique
platform for fabrication of carbon-based electrodes for electroche-
mical sensing. Briefly, the fabrication process takes the desired
filament material and extrudes it (i.e., squeezes out) through a heated
nozzle that reaches the glass transition temperature for the material
causing it to temporarily liquify, allowing it to be extruded into
layers which can be quickly cooled and resolidified. As each new
layer builds upon the previously extruded layer, the semi-liquid form
fuses to the preceding layer before solidifying. Sacrificial support
structures are generally used for complex designs to prevent any
deformations or print fails. FDM systems are considerably less
robust than other techniques due to the lack of chemical fusing.
Additionally, when compared to other 3D printing techniques
currently available, FDM printing has the lowest resolution.87
Although resolution is printer dependent, extruder nozzles are the
primary mechanism for adjusting resolution (i.e., smaller extruder
nozzles lead to higher resolution). The feature resolution of FDM is
typically on the order of 500 μm. The primary benefits of FDM
printing which drive its utility and application are its high print-
material versatility and its low-cost. Since the filaments are extruded
through controllable nozzles, multiple nozzles can be outfitted to the
device, allowing for simultaneous multi-material printing.88–90 An
FDM printer is typically much less expensive than stereolithography
(SLA) based 3D printers, which is an important consideration if the
fabricated products are to be used, for example, in point-of-care
(POC) applications.
Stereolithography.—Stereolithography (SLA) is the most foun-
dational form of 3D printing currently available and requires a
photocurable resin that polymerizes by a UV light source (com-
monly a UV laser).91 There are two configurations of SLA printing:
i) a conventional geometry, otherwise known as a “free platform
configuration” and ii) an inverted geometry, also known as a “top-
down configuration.” In the free platform configuration, the desired
structure is printed on a build platform that begins at the top of a
reservoir tank (containing the photocurable resin) and moves down-
ward into the resin after each layer is printed, until the pre-
determined number of layers have formed. The top-down config-
uration uses a platform which begins immersed at the bottom of the
reservoir tank, near a transparent optical window, where the
photocurable resin is cured layer by layer as the platform is raised
from the optical window. A movable laser (or a fixed laser with
mirrors) is used to polymerize the resin at the working surface into a
solid form. Each 2D layer solidifies and melds into the previous
layer, creating a continuous solid object. Interestingly, many
alternate forms of SLA are reported in the literature.92–94 For
example, a modification of the laser optics of conventional SLA
3D printers to a system known as two-photon polymerization (2PP)
greatly improves the feature resolution, down to the nanometer scale.
Here, a laser sends pulses that initiate two-photon absorption and
polymerization on a very small volume of the photopolymer. Of all
the 3D printing techniques currently available, 2PP has the best
resolution and is appropriate to create high-quality optical surfaces
and microstructures of considerable complexity.95 Unfortunately,
2PP has two major drawbacks prohibiting its widescale use: i) a
potentially insurmountable high cost (price) and ii) the advanced
technical knowledge required for end users. Another modified SLA
type 3D printing technique is digital light processing stereolitho-
graphy (SLA-DLP), which uses a digital micromirror as the laser
source projector. Using the digital micromirror as the projector can
simultaneously impinge upon and polymerize the entire build
surface as opposed to rastering with a single source, significantly
increasing build speed.96 Other variations of SLA that have been
developed and reported in the literature include modifications such
as incorporating an infrared (IR) laser and thermally curable resins.97
It should be noted that relying on photocuring resins as the
fundamental operating principle, limits the range of materials that
SLA-type systems can print (compared to other techniques), as
polymers such as polyethylene glycol diacrylate (PEG-DA)98 or
polymethyl methacrylate (PMMA)99 typify the type of materials
used. Good resolution and the rigid construction offered by SLA
make SLA the most standard method of fabricating in 3D printed
devices in research settings.100
Selective laser sintering.—Selective laser sintering (SLS) was
the first powder-based 3D printing technique. SLS relies on a CO2
 ECS Sensors Plus, 2022 1 010602

Figure 4. (a) Schematic representation of the 3D printing fabrication of ISMs and ISEs. (b) Schematic illustration of a solid contact ISEs and (c) a liquid contact
ISE. (d) Schematic of a paper-based device incorporating a 3D printed ISM and (e) a 4-point calibration curve for the analysis of the tetrabutylammonium cation.
Modified from D. L. Glasco, N. H. B. Ho, A. M. Mamaril, and J. G. Bell, Anal. Chem., 93, 15826 (2021). Copyright 2022 with permission from American
Chemical Society.

laser to selectively sinter (or melt) a fine powder at the active to re-spread a fresh powder coating onto the surface for the
fabrication surface.101 The fabrication surface (i.e., build platform) fabrication of the subsequent layer. SLS based printers commonly
can then be lowered, allowing for a roller (from a powder container) have print resolutions around 100 μm, which is fundamentally

Figure 5. (a) CAD schematic representation of a helical stainless-steel electrode. (b) 3D-stainless steel electrode, (c) 3D-Au plated electrode and (d) 3D-Bi
plated electrode printed using SLS fabrication. Scale bar represents 1 cm. Reproduced from K. Y. Lee, A. Ambrosi, and M. Pumera, Electroanalysis, 29(11),
2444 (2017). Copyright 2022 with permission from Electroanalysis.
 ECS Sensors Plus, 2022 1 010602
Figure 6. (a) Schematic of a 3D printed electrochemical COVID-19 immunosensor fabrication process. (b) Indirect competitive assay used for detecting the
COVID-19 recombinant protein. Reproduced from J. Munoz and M. Pumera, Chem. Engineering J., 425, 131433 (2021). Copyright 2022 with permission from
Elsevier.
determined by the particle size of the active layer as well as the focal
spot of the laser, similar to SLA printing.102 Among the main
categories of 3D printing types (e.g., FDM, SLA, and SLS), SLS
routinely delivers the strength and durability of standard industrially
fabricated parts, and the products usually retain the properties of the
bulk materials. Components made of metal or metal alloys are best
suited to SLS. The sequential addition of new layers of powder
makes SLS quite capable of multi-material printing, adding extra
levels of complexity to a design.103 Significant limitations for
printing polymer microfluidic or optical components arise from
un-sintered material that remains on the surface or in small channels,
along with the higher inherent surface roughness of the technique.
Table I compares the various 3D printing technologies (e.g., FDM,
SLA and SLS) with respect to their advantages, cost, types of
printable materials and resolution range.
Electrochemical Sensors
Ready-to-use sensing elements.—For the purposes of this re-
view, “ready-to-use” sensing elements (e.g., electrodes, membranes,
etc) are defined as being untreated/unmodified (e.g., activated,
complexed, coated, etc) prior to use. The attachment or incorpora-
tion of the “as-printed” sensing element into a device or sensor
housing does not preclude its classification as “ready-to-use.” As
mentioned previously, 3D printing has influenced many fields with
the ability to rapidly incorporate and print low-cost material to
fabricate customizable structures and devices.104,105 In the realm of
analytical electrochemistry, 3D printing was primarily used for
creating electrode housings,106 scaffolds,107 structures,108 etc, due
to the ease in which one could print rigid and nonconductive
materials. However, over the past ∼5 years, 3D printing has
exploded into the field of electroanalysis owing to advancements
relating to the printability of conductive polymers and plastics.109,110
3D printing has provided a streamlined methodology to fabricate
conductive electrodes, and recently, ion-selective membranes
(ISMs). By far, FDM 3D printing has led the surge in the fabrication
of electrochemical sensing elements due to the ease in which
conductive material (e.g., carbon fiber, metallic nanoparticles, etc)
can be introduced into extrudable plastics. Particularly interesting is
the work of the Kokkinos group, who demonstrated this capability
using a dual extrusion process.74 This work fabricated an entirely 3D
printed sensor where a nonconductive PLA filament was used to
print the holding platform while a carbon-based PLA filament was
used to print the working, counter, and reference electrodes. Dual
extrusion FDM printing allows for multi-material fabrication simul-
taneously in a single printing process. Figure 3 illustrates the
printing process (Fig. 3a), a computer aided design of the device
(Fig. 3b), and the fully printed device (Fig. 3c).
Once fabricated, the device was used to detect caffeine and
paracetamol in both pharmaceutical tablets as well as urine. Using
the electrochemical technique of differential pulse voltammetry
(DPV), this group obtained detection limits of 2.01 μM for caffeine
and 2.84 μM for paracetamol, respectively. The Kokkinos group
demonstrated the robustness of this device by simultaneously
measuring both caffeine and paracetamol in pharmaceutical for-
mulations (96% and 101% recovery, respectively) and urine (97%
and 103% recovery, respectively). Although FDM 3D printing has
led the way with fabrication of conductive based electrochemical
sensors, SLA has begun to make an impact in fabricating sensing
components that FDM has not yet established.
Recent work by the Bell group has demonstrated the capability of
SLA 3D printing technology to fabricate ready to use ISMs.111
Previously, ISMs were primarily fabricated using polyvinyl chloride
(PVC) based membranes (to ensure structural support), however,
throughout the years several groups utilized other polymers for the
support material. This work demonstrated the novelty of 3D printing
a photocurable ISM cocktail that includes all ISM components (e.g.,
plasticizer, ion-exchanger, etc) along with a flexible acrylate based
photocurable resin. Figure 4a illustrates the 3D printing process of
the ISM and fabrication of both solid-contact and liquid-contact ion-
selective electrodes (ISEs). Proof-of-concept demonstrations fo-
cused on the model ion tetrabutylammonium which was measured
using both solid-contact (Fig. 4b) and liquid contact (Fig. 4c) ISE
configurations, as well as a paper-based ISE (Figs. 4d, 3e). The work
Table II. 3D printed electrochemical sensors used for analytical analyses.

Printed 3D Printing Detection Limit of

Component Method Material Used Post Modification Analysis Technique Analyte Range Detection References
+
Ion-Selective SLA Photocurable resin — Potentiometry TBA 8–1 × 10 4
— 111
Membrane premixed with μM
ISM components
Bilirubin 8–1 × 104 —
μM
Benzalkonium 16–1 × 104 —
μM
Potassium 61–1 × 106 —
μM
Immunoassay FDM conductive gra- Immersion in DMF then electro- Charge Transfer COVID-19 re- — 0.5 ± 0.1 119
electrode phene/PLA chemically activated followed Resistance combinant μg
by immunocomplexing protein ml−1
Pyrolyzed DLW Carbon-based photo- Pyrolysis DPV Dopamine 10–50 μM 177 ± 120
Electrodes curable resin 21 nM
Carbon FDM Nonconductive PLA — DPV Caffeine 0–116 μM 2.84 μM 74

ECS Sensors Plus, 2022 1 010602

Electrode filament (housing)
Carbon-based PLA Parcetamol 0–149 μM 2.01 μM
filament (elec-
trode)
Carbon Black FDM Carbon black PLA — DPV Serontonin — — 122
Electrode
Steel, Au, Bi SLS Stainless steel Electroplated with Au and Bi films ASV Lead 50–300 ppb 3.53 ppb 118
plated elec- powder
trodes
Cadmium 50–300 ppb 9.35 ppb
Graphene/PLA FDM PLA filament (elec- — ASV Lead 50–1500 μg 0.5 μg 113
sampling trochemical cell) l−1 l−1
electrode
Graphene/PLA fila- Antimony 50–1500 μg 1.8 μg
ment (electrode) l−1 l−1
CNT, CNTCu, FDM CNT, CNT/Cu, and — Cyclic Voltammetry Ferrocyanide — 1.2 μM 112
CNT/ZnO CNT/ZnO doped
PLA elec- PLA filament
trodes
H2O2 — 2.9 μM
NAD+ — 5.3 μM
Graphene/PLA FDM PLA Filament Electrodeposition Au film Amperometry Catechol 5.1–103 μM — 121
electrodes (housing)
Graphene/PLA fila-
ment (electrode)
Carbon-based FDM Flexible PLA (E- — Chronoamperometry Glucose 12.5–400 μM — 123
PLA E-Ring Ring housing)
Carbon-based PLA
filament (elec-
trode)
Ag doped filament Potentiometry Potassium — 124
Table II. (Continued).

ECS Sensors Plus, 2022 1 010602

Printed 3D Printing Detection Limit of
Component Method Material Used Post Modification Analysis Technique Analyte Range Detection References

Ag conduction Micro Drop casted ISMs onto electrode 100–1 × 10 5

element and Extrusion surface μM

electrode
Calcium 100–1 × 105 —
μM
Sodium 1000–1 × —
105 μM

DLW—Direct Laser Writing, DPV—Differential Pulse Voltammetry, ASV—Anodic Striping Voltammetry.

 ECS Sensors Plus, 2022 1 010602
Figure 7. (a) Fabrication schematic using CAD software and dual extrusion
FDM printing of an E-ring. (b) E-ring images with dimensions (top left),
flexibility (top right), and wearable placement and connection to a portable
potentiostat (bottom). Reproduced from V. Katseli, A. Economou, and C.
Kokkinos, Anal. Chem., 93, 3331 (2021). Copyright 2022 with permission
from American Chemical Society.
further probed the robustness of using 3D printing for fabricating
ISMs for other analytes such as i) benzalkonium, a common
preservative used in eye drops and hand sanitizer, ii) bilirubin, an
important biomarker of liver health, and iii) potassium, an important
blood electrolyte. Each ISE resulted in excellent reproducibility,
selectivity, and covered the necessary detection ranges for biologi-
cally relevant levels for each target analyte. All additives were
incorporated into the 3D printable resin prior to printing allowing for
a ready to use membrane after printing. Furthermore, the authors
demonstrated the mass-production capabilities by printing 121 disk-
shaped ISMs in approximately 30 min.
Interestingly, the Subannajui group used an FDM 3D printer to
fabricate electrodes by blending PLA with i) carbon nanotubes
(CNT), ii) CNT/copper (Cu) and iii) CNT/zinc oxide (ZnO)
composites.112 As a result, the 3D printed conductive electrodes
based on CNT/PLA composites were used to perform electronic
tongue analysis. They found that the 3D printed electrodes were
electrochemically distinct and sufficiently stable over multiple cyclic
voltammetry measurements and able to distinguish the voltammetric
signals from various electroactive species (e.g., ferrocyanide, H2O2,
and NAD+). Each sensor composition was found to provide good
limits of detection for all three species in the micromolar range with
the optimal compositions of each electrode providing limits-of-
detection (LOD) of 5.3, 2.9, and 1.2 μM for H2O2, NAD+, and
ferrocyanide respectively. This research provided a low cost and
time-efficient method while using inexpensive instrumentation
where it is beneficial for preliminary observations and on-site
investigation. The Munoz group has taken a unique approach to
fabricate ready-to-use electrochemical sensors for forensic based
studies with 3D printing. Using FDM printing they fabricated a
sampling sensor for heavy metal analysis as it relates to gunshot
residue.113 This group incorporated a 3D printed electrochemical
cell using nonconductive PLA filament (housing) and a graphene/
PLA composite filament (sampling electrode) for the sampling
working electrode. Gunshot residue was collected onto the electrode
surface which could then be added to the electrochemical cell and
analyzed through square-wave anodic stripping voltammetry. The
3D printed sensors produced dynamic ranges of 50–1500 μg l−1 and
LODs of 0.5 and 1.8 μg l−1 for Pb2+ and Sb3+, respectively.
The ability to directly use the as-fabricated sensors is highly
dependent on the purity and functionality of material being printed.
Recently, it has been found that metal impurities (e.g., Fe and Ti) in
commercially available filaments drastically influence the electro-
chemical characteristics of the corresponding 3D printed sensors.114
For example, the Pumera group found that Fe, Ti and Al impurities
in commercially available graphene/PLA composite filaments leads
to enhanced catalysis towards water splitting.115 As such, it is
imperative to fully characterize the composition of all sensors
fabricated in order to gain insights and to fully understand all
factors leading to the sensor’s activity.
Post-modified sensors.—The ability to modify electrode surfaces
with conductive polymers, nanomaterials, and biological recognition
elements (i.e., enzymes, antibodies, aptamers, etc) has been ex-
tremely rewarding in the development of electrochemical sensors
which are both sensitive and selective towards specific target
analytes.116,117 As such, electrochemical sensors have been used to
detect diverse analytes in various complex matrices such as
biological fluid (e.g., blood, urine, saliva, sweat, and tears) and
environmental samples. In this section, we highlight advancements
made in the fabrication of electrochemical sensors utilizing 3D
printed surfaces which have undergone post-processing to modify
the surface of the electrochemical sensor for specific applications.
The ability to easily modify 3D printed electrode materials has
allowed researchers to expand the list of target analytes which can be
detected using sensors fabricated using 3D printing. While an
optimal scenario would permit the printing of a sensor which
contains the complete functionality required to perform the desired
measurement, barriers in the currently available 3D printer tech-
nology need to be overcome for this to be realized.
Regardless of barriers imposed simply by printer technology, 3D
printing has still made an impact in electrochemical sensing through
post-modification of the 3D printed material. For example, SLS
printing is proving particularly useful in the fabrication of customiz-
able metallic electrodes. Research performed by the Pumera group
has provided insightful and important advancements in the 3D
printing of metallic biosensors in recent years.118 A recent study by
this group utilizes the ability of SLS printing to fabricate a unique
stainless-steel helical electrode that was post-modified using elec-
troplating. Electrodes were electroplated with gold and bismuth and
subsequently used to detect heavy metals through anodic stripping
voltammetry (ASV), a technique which is an established approach to
detect trace heavy metals.
Figure 5 displays a computer aided design of the helical design
(Fig. 5a), a steel 3D printed electrode (Fig. 5b), a gold electroplated
steel electrode (Fig. 5c), and a bismuth electroplated electrode
 ECS Sensors Plus, 2022 1 010602

Figure 8. (a) Schematic demonstration of an all-inclusive integrated wearable (AIIW) top view. (b) Image of a flexible AIIW patch including 3D printed ion
sensors along with a wearable-microfluidic sample handling (WMFSH). (c) Schematic illustration of individual components assembly into a AIIW patch. (d)
Cross-sectional schematic of a AIIW patch attached to the skin during sweat collection. (e) Schematic illustration of 3D printed electrodes, electrodes membrane,
PDMS substrate, an adhesive layer, and WMFSH unit integration into a AIIW patch. Reproduced from T. Kim, Q. Yi, E. Hoang, and R. Esfandyarpour, Adv.
Mater. Tech., 6, 2001021 (2021). Copyright 2022 with permission from Advanced Materials Technologies.

(Fig. 5d). Measurements with these novel sensors resulted in
improved reproducibility, linearity, and sensitivity compared to
conventional glassy carbon electrodes for lead and cadmium
analysis. Although glassy carbon electrodes resulted in better
limits-of-detection, this unique approach shows the potential to
compete with conventional electrode materials.
The versatility and rapid prototyping ability of 3D printing allow
researchers to address important and impactful societal concerns in a
streamlined manner. Of particular relevance is the dramatic effect that
the COVID-19 pandemic had on all aspects of society throughout the
world. Here, the ability to diagnose COVID-19 quickly and accurately
was a task that many researchers in the field of analytical chemistry
embarked upon. Munoz and Pumera applied their knowledge with 3D
printing and immunosensing to fabricate a 3D printed immunosensor for
the detection of COVID-19.119 Figure 6 displays the fabrication process
of the immunosensor with the post modified 3D printed electrode.
Utilizing the ability of FDM printing and availability of graphene-based
filament the authors developed a novel diagnostic tool to detect COVID-
19 through competitive immunocomplexes.
This device utilized electrochemical impedance spectroscopy to
determine the Δratio (i.e., Δratio = (RA − R0)/R0 where R0 and RA
is the charge transfer resistance, Rct, before and after incubation of
antibody/antigen mixture, respectively) calibration of COVID-19
protein which covered a range of 1–10 μg ml−1. Comparing the
specified protein to serum showed significant overlap with a spike
analysis that was completed that provided a 103% recovery.
While FDM 3D printers have been the primary vehicle used to
fabricate sensors, the Venton group used a unique approach to
develop a sensor used to measure dopamine levels.120 The authors
demonstrate the ability to post modify a carbon-based, non-con-
ductive material into a conductive pyrolyzed carbon electrode. Using
a photopolymerizable carbon-based resin, they first printed non-
conductive microstructures, which were converted into conductive
nano-electrodes through pyrolysis, for neurotransmitter analysis.
During pyrolysis, carbon-containing substances decompose under
high heat (in the absence of oxygen) to produce glassy carbon-like
materials with conductive properties. They were able to use the post-
modified 3D printed sensors to analyze dopamine using fast-scan
cyclic voltammetry after stimulation in an adult fly brain. These
interesting electrochemical sensors were able to reproducibly detect
stimulated dopamine from 10 to 50 μM. While SLA 3D printing has
rarely been used in the fabrication of sensors, most resins are carbon
based and can therefore be easily converted into conductive
electrodes using the pyrolysis approach.
 ECS Sensors Plus, 2022 1 010602

Figure 9. (a) DLP 3D printer diagram. (b) Schematic illustration of DLP printing for a strain sensor array. (c) Images of strain sensor array size and
compressibility. (d) Image of ECUST logo printed using MWCNT/EA composition. (e) Image of ECUST logo printed using EA material. (f) Schematic
representation for a 4 × 4 strain sensor array fabrication. (g) Image of a 4 × 4 strain sensor array. Reproduced from T. Xiao, C. Qian, R. Yin, K. Wang, Y. Gao,
and F. Xuan, Adv. Mater. Tech., 6, 2000745 (2020). Copyright 2022 with permission from Advanced Materials Technologies.

An important contribution to the aim of 3D printing entire
devices in a single print was realized by the O’Neil group, who
utilized dual extrusion FDM printing to fully 3D print an all-in-one
device consisting of a housing, microfluidic channel, and
electrodes.121 Using PLA as a nonconductive filament for the
housing that holds the microfluidic channel, and a graphene/PLA
filament O’Neil presented a device to measure catechol using
amperometry. Once the device was printed the working electrode
was post modified through the electrodeposition of a gold film. The
authors successfully measured catechol from 5.1–103 μM with
extremely reproducible results. Not only does this work provide a
3D printed sensing element, but they combine it with microfluidics
in a one-step fabrication method. While individually the sensing
components and housing/fluidic channels can be fabricated using 3D
printing, the advancement in 3D printing technology (i.e., the use of
dual extruders for multi-material printing) has only recently given
researchers the ability to simultaneously print both components. The
analytical characteristics of a variety of 3D printed electrochemical
sensors can be found in Table II.
Wearables.—Wearable sensors are rapidly emerging as effective
POC devices which can provide real-time monitoring of various
electrolytes and biomarkers found in biological fluids, most com-
monly, sweat.125,126 Indeed, 3D printing is beginning to play a
profound role in the development of such wearable devices, and here
we will discuss some important contributions relating to the
incorporation of 3D printed sensors into wearable devices. The use
of low-cost materials, simplicity in fabrication, and rapid testing
capabilities, are key characteristics that successful POC devices
contain and 3D printing has begun providing these characteristics for
wearable sensors. The Kokkinos group introduced a novel electro-
chemical glucose sensor that did not rely on any enzymatic
reactions.123
Figure 7 shows the dual extrusion FDM printing process where a
non-conductive, flexible filament is used for the ring housing while a
carbon-based filament is utilized to fabricate the conventional 3-
electrode set up (e.g., working, counter, and reference electrodes). In
using a miniature potentiostat that can be directly controlled by a
smartphone, this unique wearable sensor provides a non-invasive
detection of glucose in sweat through a self-monitoring process.
Measurements of glucose with the ring-based wearable sensor yielded
a detection range from 12.5–400 μM, without interference from
common electroactive metabolites in sweat, covering the physiological
relevant range. This approach resulted in a cost-effective, easy to use,
rapid analysis of glucose, an important biomarker of diabetes, which
can effectively be used at the point-of-care.
Another advancement in wearable sensing was demonstrated by
the Esfandyarpour group, where they fabricated a multiplexed 3D
 ECS Sensors Plus, 2022 1 010602

Figure 10. (a) Schematic representation of a multi-layered pressure sensor. (b) A 3D printing schematic using dual extrusion FDM printing for sensor
fabrication. (c) Demonstration schematic of post processing removal of support material. Reproduced from M. Alsharari, B. Chen, and W. Shu, Adv. Electron.
Mater., 8, 2100597 (2021). Copyright 2022 with permission from Advanced Electronic Materials.

printed electrochemical sensor for detection of important electrolytes
in sweat.124 Figure 8 illustrates a schematic of the wearable sensor
for Ca2+, K+, and Na+ ion detection. A polydimethylsiloxane
(PDMS) fluidic channel was used to absorb sweat into the detection
well where the 3D printed sensors and reference electrode are
housed.
The 3D printed sensor consists of a 3D printed silver-based
filament for the electrode and electrical connection where the
electrode was then modified through the addition of drop casted
ion-selective membranes for Ca2+, K+, and Na+. Each sensor was
monitored through potentiometric measurements and provided
detection ranges from 100 mM to 100 μM for potassium and calcium
while sodium provided a range of 100 mM to 1 mM. Selectivity for
each sensor showed limited interference from other common
electrolytes found in sweat. Direct sweat analysis provided stable
measurements over hundreds of seconds for each sensor. With the
implementation of fluidic channels, the ability to transfer sweat to
the sensors was accomplished with ease and could be replenished
over time while volumes of previously measured sweat could flow
out the exit wells.
While the number of wearable devices which incorporate 3D
printed sensing elements is currently sparse, the rising interest in 3D
printing, coupled with the growing interest for real-time monitoring
of important health biomarkers, suggests that fully 3D printed
wearable devices will soon be realized. In fact, several other research
groups are actively working in this area, alluding to the incorpora-
tion of their sensors into wearables.127–129 One interesting example
comes from Woo Soo Kim and his cohort that have produced many
3D printable sensors that can be easily translated to a wearable
substrate for on-body analysis.127 In a recent study Kim’s group
discusses the ability to 3D print a conductive carbon nanofiber-silver
nanowire (CNF-AgNW) ink that is integrated for an ion-selective
field effect transistor (ISFET) for the detection of several electrolytes
(e.g., K+, Ca2+, and NH4+). Kim post modified the conductive CNF-
AgNW electrode with ISMs selective for each corresponding ion.
This work provided a proof-of-concept demonstration of 3D
printable CNF-AgNW ink for the use of ISFET electrochemical
sensing. These examples highlight the potential of 3D printing to
revolutionize the fabrication of wearable sensors which are low-cost,
highly reproducible, and selective.
Physical Sensors
With the increased demand to quantify and monitor diverse
parameters, sensors capable of acquiring physical information (e.g.,
shear, pressure, temperature, etc) are becoming more ubiquitous in
society, and have begun to be integrated into wearable consumer
electronics,130 soft robots,131 electronic skins,132 and smart medical
 ECS Sensors Plus, 2022 1 010602
Figure 11. Sensor readings for a pneumatic gripper embedded with strain sensors across S1, S2, and S3 for a (a) plastic strawberry, (b) pencil, (c) can of spam,
(d) toy peg, and (e) plastic banana in a 3D perspective (f) and 2D perspective (g). Reproduced from B. Shih, C. Christianson, K. Gillespie, S. Lee, J. Mayeda, Z.
Huo, and M. T. Tolley, Front. Robot. AI, 6, (2019).
prosthetics.133 As the demand for these applications grows, so do the
requirements and criteria for the development and effective im-
plementation of physical sensing devices. Physical sensors have
been developed and fabricated from different materials and
methods.134 Flexible substrates and materials have been increasingly
utilized in these applications, because of the adaptability and
conformability offered to the surfaces with different geometries
and topologies. In prior literature, piezoelectric, resistive, capacitive
and optical devices have been constructed and demonstrated, with
mechanical sensing capacities on a variety of flexible substrates,
including elastomeric nanocomposites and primarily deformable
polymeric films (e.g., polyimide/PI, polyvinylidene fluoride/PVDF
or poly(3,4-ethylenedioxythiophene): polystyrene sulfonate,
PEDOT:PSS.135 One of the prime challenges in the development
of physical sensors is the fabrication process itself, where common
approaches utilize techniques such as photolithography, lamination,
spin-coating, solution casting, vacuum filter deposition, and inkjet
printing. These techniques are often complex, not amenable to
modification, and time-consuming. As such, it is not surprising that
3D printing, with its ability to rapidly print and protype devices, has
begun to be heavily relied upon in the fabrication of physical
sensors.136
An interesting example of using 3D printing to fabricate a
flexible strain sensor, shown in Fig. 9, was published by Xiao et
al.137 Here, the authors developed a high-performance strain sensor
using a UV curable composite consisting of multiwalled carbon
nanotubes (MWCNTs) and a highly stretchable elastomer (epoxy
aliphatic acylate and aliphatic urethane diacrylate). The authors
found that the MWCNT/elastomer composite delivered a sensitivity
of 8.939 with a linearity up to 45% strain, when using 2 wt% of
MWCNTs. The sensor could measure strain between 0.01% and
60% which maintaining a high mechanical durability over 10000
cycles. As a demonstration of potential application for the 3D
printed strain sensor, the authors fabricated a 4 × 4 sensor array to
measure the distribution of external stimuli as shown in Fig. 9g.
Alsharari et al. developed a method to 3D print porous, soft
pressure sensors using an FDM printer (Fig. 10).138 The sensors,
which are composed of multiple layers, showed both a high tactile
sensitivity (0.7145 kPa−1 at 0.5 kPa) and a wide sensing range
(0.1 kPa–200 kPa). To explore the utility of the 3D printed soft,
pressure sensors, the authors investigated a variety of applications
ranging from finger bending/pressing to the addition of incremental
weights (placing a series of coins on top of the sensors). According
to the authors, such applicability coupled with the soft and flexible
nature of the sensors suggests that the sensors could be incorporated
into wearable devices or have applications in the field of robotics.
While the field of soft robotics has been dramatically influenced
by the rise in 3D printing technology, the work by the Tolley group
investigated the incorporation of 3D printed soft resistive sensors
into a soft gripper.139 As a proof-of-concept demonstration, the
authors 3D printed a soft gripper with embedded sensors and
measured the static response observed while the gripper was holding
various objects. Figures 11a–11e shows the soft gripper holding a
plastic strawberry, pencil, can of spam, toy peg and plastic banana,
respectively. Although this study highlights the versatility of 3D
printing by being able to fabricate the soft robot as well as the
corresponding sensors, the authors note that the need for high-
sensitivity electronics (to perform the measurements) as well as drift
in the observed readings need to be addressed in future research.
Table III highlights examples of 3D printed physical sensors.
Conclusions and Future Perspectives
In this review we presented several important contributions
relating to 3D printed electrochemical and physical sensors. The
explosive rise in the use of 3D printers to fabricate sensing devices is
rapidly altering the landscape in which researchers can prototype and
validate sensors. Using 3D printing to fabricate sensors has the
following primary benefits: i) precise control over shape and spatial
dimensions of the sensing elements, ii) reduced fabrication time, iii)
affordability, iv) mass production capabilities, and v) reproduci-
bility. While 3D printing has proved itself to be advantageous in the
fabrication of electrochemical and physical sensors, there are several
issues which need to be addressed before 3D printing can be used to
Table III. 3D printed physical sensors used for various applications.

3D Printing
Printed Component Method Material Used Property analyzed Range References

ECS Sensors Plus, 2022 1 010602

Capacitive Sensor FDM Thermoplastic polyurethane Temperature 10 °C–40 °C 140
AlfaOhm (PLA)-based filament with CNT
Flexible strain sensor FDM Carbon infused thermoplastic polyurethane Strain 10 N for shear 141
forces
50 N for normal
forces
Strain Sensor FDM Conductive PLA ProtoPasta filament Dynamic Strain Up to 800 Hz 142
Spatial Capacitance FDM PLA Capacitance — 143
Sensor
Soft Pressure Sensor FDM Carbon black thermoplastic polyurethane (CBTPU) Pressure 0.1–200 kPa 138
Flexible Strain Sensor DLP MWCNT/elastomer (epoxy aliphatic acrylate and aliphatic urethane Strain ∼60% strain 137
diacrylate)
 ECS Sensors Plus, 2022 1 010602
its full potential. Of particular importance is printer/material
compatibility. Currently, there are a limited number of commercially
available photocurable polymers (for SLA printers) and filaments
(for FDM printers). Simply expanding the catalogue of 3D printable
materials will lead to the fabrication of sensors with added
functionality, which will open the door for the sensing of diverse
analytes. To achieve this added functionality, active collaborations
between materials chemists and analytical chemists must be formed.
These collaborations should aim to develop filaments and resins with
new features such as the incorporation of nanomaterial, conductive
polymers, piezoelectric materials, etc. Although the technology of
3D printers has progressed to a point where many of them have
become remarkably affordable, further reductions in cost will allow
them to become more ubiquitous in academic research labs.
Furthermore, the ability to combine 3D printing mechanisms (e.g.,
SLA and FDM type printing) into a single printer will streamline
efforts towards the goal of creating complete devices in a single
print. For example, flexible wearable devices would benefit from the
ability to print electronics into flexible polymers. Interestingly, 3D
printing has also permeated the energy storage/conversion research
field, where work on the fabrication of anodes and cathodes for Li-
ion batteries and solid-state supercapacitors have already been
reported.144,145 With ongoing research and development with 3D
printing technology at the core, it is not impractical to imagine entire
sensing devices (including sensor components, interfaces, electro-
nics, power sources, etc) to be printed with a single “click.”
Considering the ability of 3D printers to deliver highly reproducible
sensors with decreased cost and fabrication time, the continued
incorporation of 3D printing into sensor design and development
will provide a much-needed gateway between academic research and
the commercialization of these sensors.
ORCID
Dalton L. Glasco https://orcid.org/0000-0002-7758-7706
Jeffrey G. Bell https://orcid.org/0000-0003-3470-1043
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